Stabilized organic material

ABSTRACT

o-Hydroxyphenyl-s-triazines of the formula I  
                 
 
     in which n is 1 to 4 and R 1  to R 7  are as defined in claim 1, can be used, in combination with sterically hindered amines of the polyalkylpiperidine type, for stabilizing organic polymers. Some of these compounds are novel and can also be used without polyalkylpiperidine.

[0001] This is a continuation-in-part application of copendingapplication Ser. No. 446,369, filed on Dec. 5, 1989.

[0002] The present invention relates to an organic material containing,as stabilizers, a mixture of a sterically hindered amine and ano-hydroxyphenyl-s-triazine, and to novel o-hydroxyphenyl-s-triazine.

[0003] It is already known from U.S. Pat. No. 4,619,956 that polymerscan be stabilized against the action of light, moisture and oxygen byadding a mixture of a sterically hindered amine and ano-hydroxyphenyl-s-triazine. The triazines used in this context containat least one phenyl group carrying a hydroxyl group in the o-position.

[0004] Triazine compounds of this type are relatively sparingly solublein many substrates and tend to migrate. In accordance with the presentinvention, similar triazine derivatives which have an improvedcompatibility with or solubility in organic polymers are used.

[0005] The invention relates to an organic material which has beenstabilized against damage caused by light, heat and oxygen and whichcontains

[0006] (a) at least one sterically hindered amine of thepolyalkylpiperidine type and

[0007] (b) at least one o-hydroxyphenyl-s-triazine, wherein the triazinecompound (b) is a compound of the formula I

[0008] in which n is 1 to 4,

[0009] R₁ and R₂ independently of one another are H, OH, C₁-C₁₂alkyl,cyclohexyl or trifluoromethyl,

[0010] R₃ and R₄ independently of one another are H, OH, C₁-C₁₂alkyl,cyclohexyl, C₁-C₁₈alkoxy or halogen and, in the event that n=1, can alsobe a radical —OR₇,

[0011] R⁵ and R₆ independently of one another are H, C₁-C₁₂alkyl orhalogen,

[0012] R₇, if n is 1, is a) C₁-C₁₈alkyl which is substituted by one ormore of the groups OH, C₁-C₁₈alkoxy, C₃-C₁₈alkenoxy, halogen, phenoxy(which is unsubstituted or substituted by C₁-C₁₈alkyl, C₁-C₁₈alkoxy orhalogen), furyloxy,

[0013]  —COOH, —COOR₈, —CONH₂, —CONHR₉, —CON(R₉)(R₁₀), —NH₂, —NHR₉,—N(R₉)(R₁₀), —NHCOR₁₁, —CN and/or by —O—CO—R₁₁,

[0014] b) C₄-C₅₀alkyl which is interrupted by one or more O and can besubstituted by OH or/and glycidyloxy,

[0015] c) C₃-C₆alkenyl,

[0016] d) glycidyl or a group

[0017] e) cyclohexyl which is unsubstituted or substituted by OH or—OCOR₁₁,

[0018] f) C₇-C₁₁phenylalkyl which is unsubstituted or substituted by OH,Cl or CH₃,

[0019] g) —CO—R₁₂ or

[0020] h) —SO₂—R₁₃,

[0021] and if n is 2, R₇ is a) C₂-C₁₆alkylene,

[0022] b) C₄-C₁₂alkenylene,

[0023] c) xylylene,

[0024] d) C₃-C₂₀alkylene which is interrupted by one or more O and/orsubstituted by OH,

[0025] e) a group —CH₂CH(OH)CH₂O—R₁₅—OCH₂CH(OH)CH₂—, —CO—R₁₆—CO—,—CO—NH—R₁₇—NH—CO— or —(CH₂)_(m)—COO—R₁₈—OOC—(CH₂)_(m)— (in which m is 1to 3) or

[0026] and if n is 3, R₇ is a group

[0027] and if n is 4, R₇ is a group

[0028] R₈ is C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₂₀alkyl which isinterrupted by one or more O, N or S and/or substituted by OH,C₁-C₄alkyl which is substituted by —P(O)(OR₁₄)₂, —N(R₉)(R₁₀) or —OCOR₁₁and/or OH, C₃-C₁₈alkenyl, glycidyl or C₇-C₁₁phenylalkyl,

[0029] R₉ and R₁₀ independently of one another are C₁-C₁₂alkyl,C₃-C₁₂alkoxyalkyl, C₄-C₁₆dialkylaminoalkyl or C₅-C₁₂cycloalkyl, or R₉and R₁₀ together are C₃-C₉alkylene or C₃-C₉oxaalkylene orC₃-C₉azaalkylene,

[0030] R₁₁ is C₁-C₁₈alkyl, C₂-C₁₈alkenyl or phenyl,

[0031] R₁₂ is C₁-C₁₈alkyl, C₂-C₁₈alkenyl, phenyl, C₁-C₁₂alkoxy, phenoxy,C₁-C₁₂alkylamino or C₆-C₁₂arylamino or a group —R₂₄—COOH or —NH—R₁₇—NCO,

[0032] R₁₃ is C₁-C₁₂alkyl, C₆-C₁₂aryl or C₇-C₁₄alkaryl,

[0033] R₁₄ is C₁-C₁₂alkyl or phenyl,

[0034] R₁₅ is C₂-C₁₀alkylene, C₄-C₅₀alkylene which is interrupted by oneor more 0, phenylene or a group -phenylene-X-phenylene- in which X is—O—, —S—, —SO₂—, —CH₂— or —C(CH₃)₂—,

[0035] R₁₆ is C₂-C₁₀alkylene, C₂-C₁₀oxaalkylene or C₂-C₁₀thiaalkylene,C₆-C₁₂arylene or C₂-C₆alkenylene,

[0036] R₁₇ is C₂-C₁₀alkylene, phenylene, tolylene, diphenylenemethane ora group

[0037] R₁₈ is C₂-C₁₀alkylene or C₄-C₂₀alkylene which is interrupted byone or more O,

[0038] R₁₉ is C₃-C₁₂alkanetriyl,

[0039] R₂₀ is C₄-C₁₂alkanetetryl,

[0040] R₂₃ is C₂-C₁₀alkylene, phenylene or a group

[0041]  wherein X is O, S, SO₂, CH₂ or C(CH₃)₂, and R₂₄ isC₂-C₁₄alkylene, vinylene or o-phenylene.

[0042] If one of the substituents in formula I is C₁-C₁₂alkyl, it can beunbranched or branched alkyl, for example methyl, ethyl, propyl,isopropyl, n-butyl, i-butyl, s-butyl or t-butyl, pentyl, hexyl, heptyl,octyl, 2-ethylhexyl, di-t-octyl, nonyl, decyl, undecyl or dodecyl. AsC₁-C₁₈alkyl, R₈, R₁₁ and R₁₂ can additionally be, for example,tetradecyl, hexadecyl or octadecyl.

[0043] As C₁-C₁₈alkoxy, R₃ and R₄ are preferably C₁-C₁₂alkoxy. Thealkoxy radical is preferably unbranched. Examples of these are methoxy,ethoxy, propoxy, butoxy, hexyloxy, octyloxy, decyloxy or dodecyloxy.

[0044] As substituted C₁-C₁₂alkyl, R₇ can be substituted by one or moreof the groups OH, C₁-C₁₈alkoxy, halogen, phenoxy which is unsubstitutedor substituted by C₁-C₁₈alkyl, C₁-C₁₈alkoxy or halogen, —COOH, —COOR₈,—CONII₂, —CONHR₉, —CON(R₉)(R₁₀), —NH₂, —NHR₉, —NH(R₉)(R₁₀), —NHCOR₁₁,—CN or —OCOR₁₁. The following groups are examples of such substitutedalkyl groups: —CH₂CH₂OH, —CH₂CH(OH)CH₃, —CH₂CH(OH)C₂H₅, —CH₂CH(OH)C₆H₁₃,—CH₂CH(OH)C₁₀H₂₁, —CH₂CH₂OCH₃—CH₂CH₂OC₂H₅, —CH₂CH₂OC₄H₉, —(CH₂)₃OH,—CH₂CH(OH)CH₂OC₄H₉, —CH₂CH(OH)CH₂OC₁₂H₂₅, —CH₂CH₂O phenyl, —CH₂CH₂Cl,—CH₂CH(OH)CH₂₀phenyl,

[0045] —CH₂COOH, —CH₂CH₂COOH, —CH₂COOC₂H₅, —CH₂COOC₈H₁₇, —CH₂CH₂COOCH₃,—CH₂CH₂COOC₄H₉, —CH₂CH₂COOC₁₂H₂₅, —CH₂CONH₂, —CH₂CONHC₄H₉,—CH₂CON(C₄H₉)₂, —CH₂CH₂CONHC₁₂H₂₅, —CH₂CH₂CON(C₂H₅)₂, —CH₂CH₂NH₂,—CH₂CH₂N(CH₃)₂, —(CH₂)₃—NH₂, —(CH₂)₃—NHC₄H₉, —(CH₂)₃N(CH₃)₂,—(CH₂)₃N(C₂H₅)₂, —(CH₂)₃NHCOCH₃, —(CH₂)₃NHCOC₇H₁₅, —CH₂CH₂CN,—CH₂CH₂OCOC₃H₇, —CH₂CH₂OCOC₁₇H₃₅, —CH₂CH(CH₃)—OCOCH₃,—CH₂CH(OCOCH₃)CH₂OC₈H₁₇ or —CH₂CH(OCOC₇H₁₅)CH₂O phenyl.

[0046] As C₃-C₆alkenyl, R₇ can, for example, be allyl, methallyl or2-butenyl. As C₃-C₁₈alkenyl, R₈ can additionally also be, for example,octenyl, dodecenyl or oleyl. As C₂-C₁₈alkenyl, R₁₁ and R₁₂ canadditionally also be vinyl.

[0047] As C₇-C₁₁phenylalkyl which is unsubstituted or substituted by OH,Cl or CH₃, R₇ and R₈ can, for example, be phenylethyl,2-hydroxy-2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl, 4-chlorobenzylor 4-methylbenzyl, but especially benzyl.

[0048] As C₂-C₁₆alkylene, R₇ can be unbranched or branched alkylene, forexample di-, tri-, tetra-, hexa-, octa-, deca- or dodeca-methylene,2,2-dimethyl-prop-1,3-ylene or 1,2-propylene. As C₄-C₁₂alkenylene, R₇can, in particular, be 2-buten-1,4-ylene. As C₃-C₂₀alkylene which isinterrupted by 0 and/or substituted by OH, R₇ can, for example, be oneof the groups —CH₂CH(OH)CH₂—, —CH₂CH₂OCH₂CH₂— or—CH₂CH(OH)CH₂O—(CH₂)_(x)—OCH₂CH(OH)CH₂— in which x=2-10.

[0049] As C₃-C₂₀alkyl which is interrupted and/or substituted by OH, R₈can, in particular, be alkyl which is substituted by OH or alkyl whichis interrupted by O and substituted by OH. Examples of these are thegroups —CH₂CH₂OH, —CH₂CH(OH)CH₃, —CH₂CH(OH)C₆H₁₃, —CH₂CH₂OC₄H₉,—CH₂CH₂OCH₂CH₂OH or —CH₂CH₂(OCH₂CH₂)_(p)OH in which p=2-9.

[0050] As C₁-C₄alkyl which is substituted by —P(O)(OR₁₄)₂, —N(R₉)(R₁₀)or —OCOR₁₁, R₉ can, for example, be —CH₂CH₂P(O)(OC₂H₅)₂,—CH₂P(O)(OC₆H₁₃)₂, —CH₂CH₂N(CH₃)₂, —CH₂CH₂CH₂N(C₂H₅)₂, —CH₂CH₂OCOC₇H₁₅or —CH₂CH₂OCOCH═CH₂.

[0051] As C₃-C₁₂alkoxyalkyl, R₉ and R₁₀ can, in particular, be2-(C₁-C₁₀alkoxy)-ethyl, for example 2-methoxyethyl, 2-butoxyethyl or2-octyloxyethyl. As C₄-C₁₆dialkylaminoalkyl, R₉ and R₁₀ can, forexample, be 2-dibutylaminoethyl, 2-diethylaminoethyl or3-dimethylaminopropyl.

[0052] As C₅-C₁₂cycloalkyl, R₉ and R₁₀ can, for example, be cyclopentyl,cyclooctyl or cyclododecyl, but especially cyclohexyl. If R₉ and R₁₀together are C₃-C₉alkylene, C₃-C₉oxaalkylene or C₃-C₉azaalkylene, theyform, together with the N atom to which they are attached, aheterocyclic ring, for example a pyrrolidine, piperidine,2,6-dimethylpiperidine, morpholine, dimethylmorpholine or piperazinering.

[0053] As C₁-C₁₂alkoxy, R₁₂ can, for example, be methoxy, ethoxy,butoxy, hexyloxy, octyloxy, decyloxy or dodecyloxy.

[0054] As C₁-C₁₂alkylamino or C₆-C₁₂arylamino, R₁₂ can, for example, behexylamino, dodecylamino, phenylamino, naphthylamino or biphenylylamino.

[0055] As C₂-C₁₀alkylene, R₁₆, R₁₇ and R₁₈ can be unbranched or branchedalkylene, for example 1,2-ethylene, tri-, tetra-, penta-, hexa-, octa-or deca-methylene, 1,2-propylene or 2,2-dimethyltrimethylene, while asoxaalkylene or thiaalkylene, R₁₆ can, for example, be 2-oxatrimethylene,3-oxapentamethylene, 3-thiapentamethylene or 2-thiatrimethylene. AsC₂-C₆alkenylene, R₁₆ can, in particular, be —CH═CH—.

[0056] As C₆-C₁₂arylene, R₁₆ and R₁₇ can, for example, be phenylene,naphthylene or biphenylene. As C₇-C₁₅alkylarylene, R₁₇ can, inparticular, be tolylene.

[0057] As C₄-C₂₀alkylene which is interrupted by O, R₁₈ can beinterrupted by 1-9 O atoms and can, in particular, be the divalentradical formed by removing the two hydroxyl groups from a polyethyleneglycol or polypropylene glycol.

[0058] In the substituents, aryl on its own or in combined radicals ispreferably phenyl, naphthyl or biphenylyl.

[0059] Compounds of the formula I which are preferred as the component(b) are those in which n is 1 to 4, R₁ and R₂ independently of oneanother are H, OH or C₁-C₄alkyl, R₃ and R₄ independently of one anotherare H, OH, C₁-C₄alkyl, C₁-C₄alkoxy, halogen or a radical —OR₇, R₅ and R₆independently of one another are H or C₁-C₄alkyl,

[0060] R₇, if n is 1, is a) C₁-C₁₈alkyl which is substituted by one ormore of the groups OH, C₁-C₁₈alkoxy, allyloxy, phenoxy, furyloxy,

[0061]  —COOR₈, —CON(R₉)(R₁₀) and/or by —OCOR₁₁,

[0062] b) C₄-C₅₀alkyl which is interrupted by one or more O and can besubstituted by OH or/and glycidyloxy,

[0063] c) allyl, glycidyl or benzyl,

[0064] d) cyclohexyl or hydroxycyclohexyl,

[0065] and if n is 2, R₇ is C₄-C₁₂alkenylene, C₄-C₆alkenylene, xylylene,C₃-C₂₀alkylene which is interrupted by one or more O and/or substitutedby OH, or R₇ is a group —CH₂CH(OH)CH₂O—R₁₅—OCH₂CH(OH)CH₂—, —CO—R₁₆—CO—,—CH₂—COO—R₁₈—OOC—CH₂— or

[0066] and if n is 3, R₇ is a group

[0067] ′and if n is 4, R₇ is a group

[0068] R₈ is C₁-C₁₂alkyl, C₃-C₁₈alkenyl, C₃-C₂₀alkyl which isinterrupted by one or more O and/or substituted by OH or R₈ isC₁-C₄alkyl which is substituted by —P(O)(OR₁₄)₂,

[0069] R₉ and R₁₀ are C₁-C₆alkyl or R₉ and R₁₀ together arepentamethylene or 3-oxapentamethylene,

[0070] R₁₁ is C₁-C₁₂alkyl, C₂-C₅alkenyl or phenyl,

[0071] R₁₄ is C₁-C₁₄alkyl,

[0072] R₁₅ is C₂-C₈alkylene, C₄-C₅₀alkylene which is interrupted by oneor more 0, or is a group

[0073] R₁₆ is C₂-C₈alkylene, C₂-C₆oxaalkylene or C₂-C₆thiaalkylene andR₁₈ is C₄-C₈alkylene or C₄-C₁₂alkylene which is interrupted by one ormore O.

[0074] R₁ and R₂ are preferably hydrogen, chlorine or C₁-C₄alkyl,particularly hydrogen or methyl. R₃ and R₄ are preferably hydrogen,chlorine or C₁-C₄alkyl, particularly hydrogen, chlorine or methyl. R₅and R₆ are preferably hydrogen.

[0075] Compounds of the formula I which are particularly preferred ascomponent (b) are those in which n is 1, 2 or 4, R₁ and R₂ independentlyof one another are H or CH₃, R₃ and R₄ independently of one another areH, CH₃ or C₁, R₅ and R₆ are hydrogen,

[0076] R₇, if n is 1, is a) C₁-C₁₄alkyl which is substituted by one ormore of the groups OH, C₁-C₁₅alkoxy, allyloxy, phenoxy, furyloxy,

[0077]  —COOR₈, —CON(R₉)(R₁₀) and/or by —OCOR₁₁,

[0078] b) C₆-C₄₅alkyl which is interrupted by one or more O and can besubstituted by OH or/and glycidyloxy,

[0079] c) glycidyl or

[0080] d) hydroxycyclohexyl,

[0081] and if n is 2, R₇ is C₆-C₁₂alkenylene, 2-butenylene-1,4,xylylene, C₃-C₂₀alkylene which is interrupted by one or more O orsubstituted by OH, or R₇ is a group —CH₂CH(OH)CH₂O—R₁₅—OCH₂CH(OH)CH₂—,—CO—R₁₆—CO—, —CH₂—COO—R₁₈—OOC—CH₂— or

[0082] and if n is 4, R₇ is

[0083] R₈ is C₄-C₁₀alkyl, oleyl, C₃-C₂₀alkyl which is interrupted by oneor more O and/or substituted by OH, or R₈ is —CH₂P(O)(OR₁₄)₂,

[0084] R₉ and R₁₀ are C₂-C₆alkyl

[0085] R₁₁ is C₆-C₁₀alkyl, C₂-C₃alkenyl

[0086] R₁₄ is C₁-C₁₄alkyl,

[0087] R₁₅ is C₂-C₈alkylene, C₁₀-C₄₅alkylene which is interrupted bymore than one 0, or is a group

[0088] R₁₆ is C₄-C₈alkylene and R₁₈ is C₄-C₈alkylene.

[0089] A further preferred group of compounds of the formula I is formedby those in which n is 1 or 2 and, if n is 1, R₇ is a group—CH₂CH(OH)CH₂—OR₂₁ in which R₂₁ is C₁-C₁₈alkyl, allyl, phenyl, furyl,C₆-C₁₂-alkanoyl or C₃-C₅alkenoyl and, if n is 2, R₇ is a group—CH₂CH(OH)CH₂O—R₁₅—OCH₂CH(OH)CH₂— in which R₁₅ is as defined above.

[0090] The following compounds are examples of individual compounds ofthe formula I

[0091] R₇=CH₂ phenyl

[0092] —CH₂CH₂OH

[0093] —CH₂CH₂OCOCH₃

[0094] —CH₂CH₂OCOCH═CH₂

[0095] —CH₂CH(OH)CH₂OC₈H₁₇

[0096] —CH₂CH(OH)CH₂O(CH₂)₁₂₋₁₄CH₃

[0097] —CH₂CH(OH)CH₂O phenyl

[0098] —CH₂CH(OH)CH₂OCOC(CH₃)═CH₂

[0099] —CH₂COOH

[0100] —CH₂CH₂COOC₄H₉

[0101] —CH₂COOC₈H₁₇

[0102] —CH₂COO(CH₂CH₂O)₇H

[0103] —CH₂COOCH₂CH(OH)CH₂OCOCH═CH₂

[0104] —CH₂COOCH₂CH(CH₃)OCH₂CH(CH₃)OCH(CH₃)CH₃

[0105] —CH₂COOCH₂P(O)(OC₂H₅)₂

[0106] —CH₂COOCH₂CH(OH)CH₂P(O)(OC₄H₉)₂

[0107] —CH₂COO(CH₂)₇CH═CHC₈H₁₇

[0108] —CH₂COOCH₂CH₂OCH₂CH₂OC₆H₁₃

[0109] —CH₂CON(C₂H₅)₂

[0110] —CH₂CONHCH₂CH₂CH₂N(CH₃)₂

[0111] —CH₂CONHC₈H₁₇

[0112] —CH₂CON(C₈H₁₇)₂

[0113] R₇=—CH₂COOC₂H₅

[0114] —CH₂COOCH₂CH₂OCH₃

[0115] —CH₂COOCH₂CH═CH-phenyl

[0116] —CH₂CH(OH)CH₂O(CH₂)₁₂₋₁₄CH₃

[0117] —CH₂COOCH₂CH(OH)CH₂OC₈H₁₇

[0118] —CH₂phenyl

[0119] —CH₂CH═CH₂

[0120] —CH₂CON(C₄H₉)₂

[0121] —CH₂CH₂CONHC₈H₁₇

[0122] —CO—OC₆H₁₃

[0123] —CH₂CH₂C₁

[0124] —CH₂CH₂CN

[0125] R₇=—CH₂CH(OH)phenyl —CH₂CH(OH)CH₂O(CH₂)₁₂₋₁₄CH₃

[0126] —CH₂CH(OH)CH₂OCOphenyl

[0127] —CH₂CH(CH₃)OCOCH₃

[0128] —SO₂—C₁₂H₁₂

[0129] —CH₂COOC₁₀H₂₁

[0130] —CH₂CONHCH₂CH₂OCH₃

[0131] —CH₂CH₂CONHCH₂phenyl

[0132] —(CH₂)₃CONH(CH₂)₃N(C₂H₅)₂

[0133] —CH₂CONHC₁₂H₂₅

[0134] R₇=—CH₂CH(OH)CH₂—

[0135] —CH₂—CH═CH—CH₂—

[0136] —(CH₂)₄—

[0137] —(CH₂)₆—

[0138] —(CH₂)₈—

[0139] —(CH₂)₁₂—

[0140] —CH₂CH(OH)CH₂O—CH₂CH₂—OCH₂CH(OH)CH₂—

[0141] —CH₂CH(OH)CH₂O—(CH₂)₆—OCH₂CH(OH)CH₂—

[0142] —CH₂COO—(CH₂)₆—OCOCH₂

[0143] R₇=—CH₂CH(OH)CH₃

[0144] —CH₂CH₂OC₄H₉

[0145] —CH₂CH₂COC₂H₅

[0146] —CH₂COOC₈H₁₇

[0147] —CH₂CH(OH)CH₂OC₄H₉

[0148] —CH₂CH(OH)CH₂O phenyl

[0149] R₇=—CH₂CH₂OH

[0150] —CH₂CH₂O phenyl

[0151] —CH₂COOC₆H₁₃

[0152] —CH₂CH₂COO(CH₂CH₂O)₃H

[0153] —CH₂CH(OH)CH₂OC₆H₁₃

[0154] —CH₂CH(OH)CH₂phenyl

[0155] Some of the triazine derivatives of the formula I are knowncompounds. Many such compounds and also their preparation and their useas UV absorbers for organic materials are described in U.S. Pat. Nos.3,244,708, 3,249,608 and 3,423,360. Their use in photographic materialsis described in U.S. Pat. No. 3,843,371.

[0156] Another fraction of the triazine derivatives constitutes novelcompounds. Compounds which are novel and are also a subject of thepresent invention are those of the formula Ia

[0157] in which n is 1 to 4,

[0158] R₁ and R₂ independently of one another are H, OH, C₁-C₁₂alkyl,cyclohexyl or trifluoromethyl,

[0159] R₃ and R₄ independently of one another are H, OH, C₁-C₁₂alkyl,cyclohexyl, C₁-C₁₈alkoxy or halogen and in the event that n=1, can alsobe a radical —OR₇,

[0160] R₅ and R₆ independently of one another are H, C₁-C₁₂alkyl orhalogen,

[0161] R₇, if n is 1, is a) C₁-C₁₂alkyl which is substituted by phenoxy(which is unsubstituted or substituted by C₁-C₁₈alkyl, C₁-C₁₈alkoxy orhalogen) or by a group

[0162] —COOR₈, —CONH₂, —CONH , —CON(R₉)(R₁₀), —NH₂, NHR₉, —N(R₉)(R₁₀) or—O—CO—R₂₂,

[0163] b) C₄-C₅₀alkyl which is interrupted by more than one O and can besubstituted by OH or/and glycidyloxy,

[0164] be substituted by OH or/and glycidyloxy,

[0165] d) cyclohexyl substituted by OH or —OCOR₁₁

[0166] e) a group —CH₂CH(OH)CH₂OR₂₁

[0167] f) a group —SO₂—R₁₃,

[0168] g) a group —CO—R₁₂,

[0169] and if n is 2, R₇ is

[0170] a) C₂-C₁₂alkylene,

[0171] b) C₄-C₁₂alkenylene,

[0172] c) xylylene,

[0173] d) C₃-C₂₀alkylene which is interrupted by one or more 0 and/orsubstituted by OH,

[0174] e) a group —CH₂CH(OH)CH₂O—R₁₅—OCH₂CH(OH)CH₂—,—(CH₂)_(m)—COO—R₁₈—OOC—(CH₂)_(m)— (wherein m is 1-3) or

[0175] and if n is 3, R₇ is a group

[0176]  (wherein m is 1-3),

[0177] and if n is 4, R₇ is a group

[0178]  (wherein m is 1-3),

[0179] R₉ is C₃-C₂₀alkyl which is interrupted by one or more O, N or Sand can be substituted by OH, or R₈ is C₁-C₄alkyl which is substitutedby —P(O)(OR₁₄)₂, —N(R₉)(R₁₀), or —OCOR₁₁ and/or OH, or R₈ isC₃-C₁₈alkenyl, glycidyl or C₇-C₁₁phenylalkyl,

[0180] R₉ and R₁₀ independently are C₁-C₁₂alkyl, C₃-C₁₂alkoxyalkyl,C₄-C₁₆dialkylaminoalkyl or C₅-C₁₂cycloalkyl, or R₉ and R₁₀ together areC₃-C₉alkylene or C₃-C₉-oxaalkylene or C₃-C₉azaalkylene,

[0181] R₁₁ is C₁-C₁₈alkyl, C₂-C₁₈alkenyl or phenyl,

[0182] R₁₂ is a group —R₂₄—COOH or —NH—R₁₇—NCO,

[0183] R₁₃ is C₁-C₁₂alkyl, C₆-C₁₂aryl or C₇-C₁₄alkaryl

[0184] R₁₄ is C₁-C₁₂alkyl or phenyl

[0185] R₁₅ is C₂-C₁₀alkylene, C₄-C₅₀alkylene which is interrupted by oneor more 0, or R₁₅ is phenylene or a group -phenylene-X-phenylene- inwhich X is —O—, —S—, —SO₂—, —CH₂— or —C(CH₃)₂—,

[0186] R₁₇ is C₂-C₁₀alkylene, phenylene, tolylene, diphenylenemethane ora group

[0187] R₁₈ is C₂-C₁₀alkylene or C₄-C₂₀alkylene which is interrupted byone or more O,

[0188] R₁₉ is C₃-C₁₂alkanetriyl,

[0189] R₂₀ is C₄-C₁₂alkanetetryl,

[0190] R₂₁ is H, C₁-C₁₈alkyl, C₃-C₁₈alkenyl, phenyl, phenyl substitutedby C₁-C₁₂alkyl, C₁-C₁₂alkoxy or halogen, or R₂₁ is C₂-C₁₉alkanoyl,benzoyl, C₃-C₁₈alkenoyl, furyl or a group

[0191] R₂₂ is C₂-C₅alkenyl,

[0192] R₂₃ is C₂-C₁₀alkylene, phenylene or a group

[0193]  wherein X is O, S, SO₂, CH₂ or C(CH₃)₂, and

[0194] R₂₄ is C₂-C₁₄alkylene, vinylene or o-phenylene.

[0195] Amongst these compounds of the formula Ia, preferred compoundsare those in which n is 1 to 4, R₁ and R₂ independently of one anotherare H, OH or C₁-C₄alkyl, R₃ and R₄ independently of one another are H,OH, C₁-C₄alkyl, C₁-C₄alkoxy, halogen or a radical —OR₇, R₅ and R₆independently of one another are H or C₁-C₄alkyl,

[0196] R₇, if n is 1, is C₁-C₆alkyl which is substituted by —COOR₈,—COONHR₉, —CON(R₉)(R₁₀) or —OCOR₂₂, or R₇ is glycidyl, hydroxycyclohexylor a group —CH₂CH(OH)CH₂OR₂₁, and if n is 2, R₇ is C₄-C₁₂alkylene,C₄-C₆alkenylene, xylylene, C₃-C₂₀alkylene which is interrupted by one ormore O and/or substituted by OH, or R₇ is a group—CH₂CH(OH)CH₂O—R₁₅—OCH₂CH(OH)CH₂—, —CH₂—COO—R₁₈—OOCCH₂— or

[0197] and if n is 3, R₇ is a group

[0198] and if n is 4, R₇ is a group

[0199] R₈ is C₃-C₂₀alkyl which is interrupted by one or more O and canbe substituted by OH or

[0200] R₈ is C₁-C₄alkyl which is substituted by —P(O)(OR₁₄)₂ or R₈ isC₃-C₁₈alkenyl,

[0201] R₉ and R₁₀ independently are C₁-C₈alkyl or cyclohexyl or R₉ andR₁₀ together are pentamethylene or 3-oxapentamethylene,

[0202] R₁₄ is C₁-C₁₄alkyl,

[0203] R₁₅ is C₂-C₈alkylene, C₄-C₅₀alkylene which is interrupted by oneor more 0, or R₁₅ is a group -phenylene-X-phenylene- in which X is —O—,—CH₂— or —C(CH₃)₂—,

[0204] R₁₈ is C₄-C₈alkylene or C₄-C₁₂alkylene which is interrupted byone or more 0,

[0205] R₂₁ is H, C₄-C₁₈alkyl, allyl, phenyl, fury!; C₅-C₁₉alkanoyl orC₃-C₅alkenoyl and R₂₂ is C₂-C₅alkenyl, in particular those in which n is1, 2 or 4, R₁ and R₂ independently of one another are H or CH₃, R₃ andR₄ independently of one another are H, CH₃ or C₁, R₅ and R₆ arehydrogen,

[0206] R₇, if n is 1, is C₁-C₄alkyl which is substituted by —COOR₈,—CON(R₉)(R₁₀) or —O—COR₂, or R₇ is glycidyl, 2-hydroxycyclohexyl or agroup —CH₂CH(OH)CH₂OR₂₁,

[0207] and if n is 2, R₇ is C₆-C₁₂alkenylene, 2-butene-1,4-ylene,xylylene or C₃-C₂₀alkylene which is interrupted by one or more O and/orsubstituted by OH, or R₇ is a group —CH₂CH(OH)CH₂O—R₁₅—OCH₂CH(OH)CH₂—,—CH₂—COO—R₁₈—OOCCH₂— or

[0208] and if n is 4, R₇ is a group

[0209] R₈ is C₃-C₂₀alkyl which is interrupted by one or more O and canbe substituted by OH or R₈ is —CH₂P(O)(OR₁₄)₂ or oleyl

[0210] R₉ and R₁₀ are C₂-C₆alkyl

[0211] R₁₅ is C₂-C₈alkylene, C₁₀-C₄₅alkylene which is interrupted by oneor more 0 or is a group

[0212] R₁₈ is C₄-C₈alkylene,

[0213] R₂₁ is H, C₄-C₁₅alkyl, allyl, phenyl, furyl, C₅-C₁₂alkanoyl orC₃-C₅alkenoyl

[0214] and R₂₂ is C₂-C₃alkenyl.

[0215] The compounds of the formula Ia in which n is 2 are alsopreferred.

[0216] In general, the compounds of the formula I and la can be preparedby introducing the radical R₇ into the p-hydroxyl group in a compound ofthe formula II

[0217] The compounds of the formula II are known compounds and can beprepared by a Friedel-Crafts reaction between cyanuric chloride and 1mole of an aromatic compound of the formula

[0218] and 1 mole of an aromatic compound of the formula

[0219] and 1 mole of resorcinol, as described, for example, in SwissPatent 480,091 or in Swiss Patent 484,695 or in U.S. Pat. No. 3,244,708.

[0220] The conversion of II into I can be effected by various processesknown per se, depending on the nature of the radical R₇i If R₇ issubstituted alkyl, alkenyl, glycidyl, phenylalkyl, —CO—R₁₂, —SO₂—R₁₃,alkylene, alkenylene, xylylene or —COR₁₆CO—, the compound II or analkali metal salt thereof can be reacted with a halogen compound of theformula Hal-R₇ or Hal-R₇-Hal in which Hal is chlorine, bromine oriodine, in particular with the compounds Cl—R₇ and Cl-R₇—Cl.

[0221] If R₇ is a group

[0222] in which R′ is hydrogen or CH₃ and Y is —COOR₈, —CONH₂, —CONHR₉,—CON(R₉)(R₁₀) or —CN, the compounds can be prepared by reacting acompound of the formula II with a compound of the formula

[0223] in the manner of a so-called Michael addition reaction.

[0224] If R₇ is a group —CH₂CH(OH)—W in which W is alkyl, phenyl,phenylalkyl or —CH₂OR₂₁, such compounds can be prepared by reacting acompound of the formula II with an epoxide of the formula

[0225] Analogously, compounds of the formula I in which n is 2 and R₇ isa group —CH₂CH(OH)CH₂O—R₁₅—OCH₂CH(OH)CH₂—, can be prepared by reacting 2moles of a compound II and 1 mole of a bis-glycidyl ether of the formula

[0226] Compounds of the formula I in which R₇ is cyclohexyl substitutedby OH can be prepared by reaction of II with cyclohexene oxide.

[0227] Compounds of the formula I in which n is 2 and R₇ is—CO—NH—R₁₇—NH—CO— can be prepared by reacting 2 moles of a compound ofthe formula II with 1 mole of a diisocyanate OCN—R₁₇—NCO. Compounds ofthe formula I in which n is 2 and R₇ is a group —CH₂CH(OH)CH₂— can beprepared by reacting 2 moles of a compound II with 1 mole ofepichlorohydrin.

[0228] Compounds of formula I or Ia wherein n is 1 and R₇ is a group

[0229] or a group —CO—R₂₄—COOH or —CONH—R₁₇—NCO can be prepared from IIby reaction with one molar equivalent of a compound R₂₃

[0230] or OCN—R₁₇—NCO respectively.

[0231] It is also possible to convert a compound of the formula I intoanother compound of the formula I. For example, a hydroxyalkyl oraminoalkyl radical R₇ can be converted by acylation with R₁₁COCl intothe corresponding acyloxy or acylamino derivative.

[0232] Or a cyanoalkyl radical R₇ can be converted by reduction into anaminoalkyl radical.

[0233] Compounds in which R₇ is alkyl which is substituted by —COOR₈ canbe transesterified with another alcohol or polyol.

[0234] The methods required for the individual stages of the synthesisare known to those skilled in the art; some of them are described ingreater detail in the examples which follow later.

[0235] The polyalkylpiperidines used as the component (a) preferablycontain at least one group of the formula

[0236] in which R is hydrogen or methyl. R is preferably hydrogen. Theseare derivatives of polyalkylpiperidines, in particular of2,2,6,6-tetramethylpiperidine. These compounds preferably carry one ortwo polar substituents or a polar spiro ring system in the 4-position ofthe piperidine ring. These compounds can be low-molecular or oligomericor polymeric compounds.

[0237] The following classes of polyalkylpiperidines are of particularimportance.

[0238] a) Compounds of the formula m

[0239] in which n is a number from 1 to 4, R is hydrogen or methyl, R₃₁is hydrogen, amine oxide, hydroxyl, C₁-C₁₂alkyl, C₃-C₈alkenyl,C₃-C₈alkinyl, C₇-C₁₂aralkyl, C₁-C₁₈alkoxy, C₅-C₈cycloalkoxy,C₇-C₉phenylalkoxy, C₁-C₈alkanoyl, C₃-C₅alkenoyl, C₁-C₁₈alkanoyloxy,benzyloxy, glycidyl or a group —CH₂CH(OH)-Z, in which Z is hydrogen,methyl or phenyl, R₃₁ being preferably H, C₁-C₄alkyl, allyl, benzyl,acetyl or acryloyl, and, if n is 1, R₃₂ is hydrogen, C₁-C₁₈alkyl whichcan be interrupted by one or more oxygen atoms, cyanoethyl, benzyl,glycidyl, a monovalent radical of an aliphatic, cycloaliphatic,araliphatic, unsaturated or aromatic carboxylic acid, carbamic acid oran acid containing phosphorus or a monovalent silyl radical, preferablya radical of an aliphatic carboxylic acid having 2 to 18 C atoms, acycloaliphatic carboxylic acid having 7 to 15 C atoms, anα,β-unsaturated carboxylic acid having 3 to 5 C atoms or an aromaticcarboxylic acid having 7 to 15 C atoms, or, if n is 2, isC₁-C₁₂alkylene, C₄-C₁₂alkenylene, xylylene, a divalent radical of analiphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid,dicarbamic acid, or acid containing phosphorus, or a divalent silylradical, preferably a radical of an aliphatic dicarboxylic acid having 2to 36 C atoms, a cycloaliphatic or aromatic dicarboxylic acid having8-14 C atoms or an aliphatic, cycloaliphatic or aromatic dicarbamic acidhaving 8-14 C atoms, or, if n is 3, is a trivalent radical of analiphatic, cycloaliphatic or aromatic tricarboxylic acid, an aromatictricarbamic acid or an acid containing phosphorus, or a trivalent silylradical, and, if n is 4, is a tetravalent radical of an aliphatic,cycloaliphatic or aromatic tetracarboxylic acid.

[0240] Examples of possible C₁-C₁₂alkyl substituents are methyl, ethyl,n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl,2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

[0241] As C₁-C₁₈alkyl, R₃₁ or R₃₂ can be the groups defined above andadditionally, for example, n-tridecyl, n-tetradecyl, n-hexadecyl orn-octadecyl.

[0242] As C₃-C₈alkenyl, R₃₁ can, for example, be 1-propenyl, allyl,methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl,4-tert-butyl-2-butenyl.

[0243] As C₃-C₈alkinyl, R₃₁ is preferably propargyl.

[0244] As C₇-C₁₂aralkyl, R₃₁ is especially phenethyl and, in particular,benzyl.

[0245] Examples of R₃₁ as C₁-C₈alkanoyl are formyl, propionyl, butyrylor octanoyl, but preferably acetyl, and examples of R₂₁ as C₃-C₅alkenoylare especially acryloyl.

[0246] Examples of R₃₁ as C₁-C₁₈alkoxy are hexyloxy, heptyloxy, octyloxyor decyloxy. As cycloalkoxy, R₃₁ is preferably cyclohexyloxy. Asphenylalkoxy, R₃₁ is preferably benzyloxy. Examples of R₃₁ asalkanoyloxy are acetoxy, butyroyloxy, hexanoyloxy, octanoyloxy,decanoyloxy or stearoyloxy.

[0247] Examples of R₃₂ as a monovalent radical of a carboxylic acid area radical of acetic acid, caproic acid, stearic acid, acrylic acid,methacrylic acid, benzoic acid orβ-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid.

[0248] Examples of R₃₂ as a divalent radical of a dicarboxylic acid area radical of malonic acid, succinic acid, glutaric acid, adipic acid,suberic acid, sebacic acid, maleic acid, itaconic acid, phthalic acid,dibutylmalonic acid, dibenzylmalonic acid,butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)-malonic acid orbicycloheptenedicarboxylic acid.

[0249] Examples of R₃₂ as a trivalent radical of a tricarboxylic acidare a radical of trimellitic acid, citric acid or nitrilotriacetic acid.

[0250] Examples of R₃₂ as a tetravalent radical of a tetracarboxylicacid are the tetravalent radical of butane-1,2,3,4-tetracarboxylic acidor pyromellitic acid.

[0251] Examples of R₃₂ as a divalent radical of a dicarbamic acid are aradical of hexamethylenedicarbamic acid or 2,4-toluylenedicarbamic acid.

[0252] Preferred compounds of the formula m are those in which R ishydrogen, R₃₁ is hydrogen or methyl, n is 1 and R₃₂ is C₁-C₁₈alkyl, or nis 2 and R₃₂ is the diacyl radical of an aliphatic dicarboxylic acidhaving 4-12 C atoms.

[0253] The following compounds are examples of polyalkylpiperidinecompounds of this class:

[0254] 1) 4-Hydroxy-2,2,6,6-tetramethylpiperidine,

[0255] 2) 1-Allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,

[0256] 3) 1-Benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,

[0257] 4)1-(4-tert-Butyl-2-butenyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine,

[0258] 5) 4-Stearoyloxy-2,2,6,6-tetramethylpiperidine,

[0259] 6) 1-Ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine,

[0260] 7) 4-Methacryloyloxy-1,2,2,6,6-pentamethylpiperidine,

[0261] 8) 1,2,2,6,6-Pentamethylpiperidin-4-ylβ-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate,

[0262] 9) Di-(1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl) maleinate,

[0263] 10) Di-(2,2,6,6-tetramethylpiperidin-4-yl) succinate,

[0264] 11) Di-(2,2,6,6-tetramethylpiperidin-4-yl) glutarate,

[0265] 12) Di-(2,2,6,6-tetrmethylpiperidin-4-yl) adipate,

[0266] 13) Di-(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,

[0267] 14) Di-(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,

[0268] 15) Di-(1,2,3,6-tetrarethyl-2,6-diethyl-piperidin-4-yl) sebacate,

[0269] 16) Di-(1-allyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate,

[0270] 17) 1-Hydroxy-4—cyanoethyloxy-2,2,6,6-tetramethylpiperidine,

[0271] 18) 1-Acetyl-2,2,6,6-tetramethylpiperidin-4-yl acetate,

[0272] 19) Tri-(2,2,6,6-tetramethylpiperidin-4-yl) trimellitate,

[0273] 20) 1-Acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine,

[0274] 21) Di-(2,2,6,6-tetrmethylpiperidin-4-yl) diethylmalonate,

[0275] 22) Di-(1,2,2,6,6-pentamethylpiperidin-4-yl) dibutylmalonate,

[0276] 23) Di-(1,2,2,6,6-pentamethylpiperidin-4-yl)butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)-malonate,

[0277] 24) Di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,

[0278] 25)Di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate,

[0279] 26)Hexane-1′,6′-bis-(4-carbamoyloxy-1-n-butyl-2,2,6,6-tetramethylpiperidine),

[0280] 27)Toluene-2′,4′-bis-(4-carbamoyloxy-1-n-propyl-2,2,6,6-tetramethylpiperidine),

[0281] 28) Tetra-(2,2,6,6-tetramethylpiperidin-4-yl)butane-1,2,3,4-tetracarboxylate,

[0282] 29) Tetra-(1,2,2,6,6-pentamethylpiperidin-4-yl)butane-1,2,3,4-tetracarboxylate,

[0283] 30) Tris-(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphite,

[0284] 31) Tris-(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphate,

[0285] 32)Phenyl-[bis-(1,2,2,6,6-pentamethylpiperidin-4-yl)]phosphonate,

[0286] 33) 4-Hydroxy-1,2,2,6,6-pentamethylpiperidine,

[0287] 34) 4-Hydroxy-N-hydroxyethyl-2,2,6,6-tetramethylpiperidine,

[0288] 35) 4-Hydroxy-N-(2-hydroxypropyl)-2,2,6,6-tetramethylpiperidine,

[0289] 36) 1-Glycidyl-4-hydroxy-2,2,6,6-tetramethylpiperidine.

[0290] b) Compounds of the formula IV

[0291] in which n is the number 1 or 2, R and R₃₁ are as defined undera), R₃₃ is hydrogen, C₁-C₁₂alkyl, C₂-C₅hydroxyalkyl, C₅-C₇cycloalkyl,C₇-C₈aralkyl, C₂-C₁₈alkanoyl, C₃-C₅alkenoyl, benzoyl or a group of theformula

[0292] and, if n is 1, R₃₄ is hydrogen, C₁-C₁₈alkyl, C₃-C₈alkenyl,C₅-C₇cycloalkyl, C₁-C₄alkyl which is substituted by a hydroxyl, cyano,alkoxycarbonyl or carbamide group, glycidyl or a group of the formula—CH₂—CH(OH)-Z or of the formula —CONH-Z in which Z is hydrogen, methylor phenyl or R₃₄ is a group —CO—CO—NH—(C₁-C₁₈alkyl); or, if n is 2, R₃₄is C₂-C₁₂alkylene, C₆-C₁₂arylene, xylylene, a —CH₂—CH(OH)—CH₂— group ora group —CH₂—CH(OH)—CH₂—O-D-O— in which D is C₂-C₁₀alkylene,C₆-C₁₅arylene or C₆-C₁₂cycloalkylene or, provided that R₃₃ is notalkanoyl, alkenoyl or benzoyl, R₃₄ can also be a divalent radical of analiphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamicacid or the group —CO—, or, if n is 1, R₃₃ and R₃₄ together can be thedivalent radical of an aliphatic, cycloaliphatic or aromatic1,2-dicarboxylic or 1,3-dicarboxylic acid.

[0293] Possible C₁-C₁₂alkyl or C₁-C₁₈alkyl substituents are as alreadydefined under a).

[0294] Possible C₅-C₇cycloalkyl substituents are especially cyclohexyl,

[0295] As C₇-C₈aralkyl, R₃₃ is especially phenylethyl or, in particular,benzyl. As C₂-C₅hydroxyalkyl, R₃₃ is especially 2-hydroxyethyl or2-hydroxypropyl.

[0296] Examples of R₃₃ as C₂-C₁₈alkanoyl are propionyl, butyryl,octanoyl, dodecanoyl, hexadecanoyl or octadecanoyl, but preferablyacetyl, and examples of R₃₃ as C₃-C₅alkenoyl are especially acryloyl.

[0297] Examples of R₃₄ as C₂-C₈alkenyl are allyl, methallyl, 2-butenyl,2-pentenyl, 2-hexenyl or 2-octenyl.

[0298] Examples of R₃₄ as C₁-C₄alkyl which is substituted by a hydroxyl,cyano, alkoxycarbonyl or carbamide group are 2-hydroxyethyl,2-hydroxypropyl, 2-cyanoethyl, methoxy-carbonylmethyl,2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or2-(dimethylamino-carbonyl)-ethyl.

[0299] Examples of possible C₂-C₁₂alkylene substituents are ethylene,propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene,octamethylene, decamethylene or dodecamethylene.

[0300] Examples of possible C₆-C₁₅arylene substituents are o-, m- orp-phenylene, 1,4-naphthylene or 4,4′-biphenylene.

[0301] As C₆-C₁₂cycloalkylene, D is especially cyclohexylene.

[0302] Preferred compounds of the formula IV are those in which n is 1or 2, R is hydrogen, R₃, is hydrogen or methyl, R₃₃ is hydrogen,C₁-C₁₂alkyl or a group of the formula

[0303] and, in the event that n=1, R₃₄ is hydrogen or C₁-C₁₂alkyl and,in the event that n=2, R₃₄ is C₂-C₈alkylene.

[0304] The following compounds are examples of polyalkylpiperidinecompounds of this class:

[0305] 37)N,N′-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-hexamethylene-1,6-diamine,

[0306] 38)N,N′-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-hexamethylene-1,6-diacetamide,

[0307] 39) Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-amine,

[0308] 40) 4-Benzoylamino-2,2,6,6-tetramethylpiperidine,

[0309] 41)N,N′-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-N,N′-dibutyladipamide,

[0310] 42)N,N′-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-N,N′-dicyclohexyl-2-hydroxypropylene-1,3-diamine,

[0311] 43)N,N′-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-p-xylylenediamine,

[0312] 44) N,N′-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-succindiamide,

[0313] 45) N-(2,2,6,6-Tetramethylpiperidin-4-yl)-o-aminopropionic aciddodecyl ester,

[0314] 46) The compound of the formula

[0315] 47)N-(1-Octyloxy-2,2,6,6tetramethylpiperidin-4-yl)-N′-dodecyl-oxalamide

[0316] 48) N-(2,2,6,6-Tetrarethylpiperidin-4-yl)-α-dodecylsuccinimide,

[0317] 49) 4-Methacrylamido 1,2,2,6,6-pentamethylpiperidine.

[0318] c) Compounds of the formula V,

[0319] in which n is the number 1 or 2, R and R₃₁ are as defined undera) and, if n is 1, R₃₅ is C₂-C₈alkylene or C₂-C₈hydroxyalkylene orC₄-C₂₂acyloxyalkylene and, if n is 2, R₃₅ is the group (—CH₂)₂C(CH₂—)₂.

[0320] Examples of R₃₅ as C₂-C₈alkylene or C₂-C₈hydroxyalkylene areethylene, 1-methylethylene, propylene, 2-ethylpropylene or2-ethyl-2-hydroxymethylpropylene.

[0321] An example of R₃₅ as C₄-C₂₂acyloxyalkylene is2-ethyl-2-acetoxymethylpropylene.

[0322] The following compounds are examples of polyalkylpiperidinecompounds of this class:

[0323] 50) 9-Aza-8,8,10,10-tetramethyl-1,5-dioxaspiro[5.5]undecane,

[0324] 51)9-Aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro[5.5]undecane,

[0325] 52) 8-Aza-2,7,7,8,9,9-hexamethyl-1,4-dioxaspiro[4.5]decane,

[0326] 53)9-Aza-3-hydroxymethyl-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxaspiro[5.5]undecane,

[0327] 54)9-Aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,10,10-tetramethyl-1,5-dioxaspiro[5.5]undecane,

[0328] 55)2,2,6,6-Tetramethylpiperidin-4-spiro-2′-(1′,3′-dioxane)-5′-spiro-5″-(1″,3″-dioxane)-2″-spiro-4′″-(2′″,2′″,6′″,6′″-tetramethylpiperidine).

[0329] d) Compounds of the formulae VIA, VIB and VIC

[0330] in which n is the number 1 or 2, R and R₃₁ are as defined undera), R₃₆ is hydrogen, C₁-C₁₂alkyl, allyl, benzyl, glycidyl orC₂-C₆alkoxyalkyl and, if n is 1, R₃₇ is hydrogen, C₁-C₁₂alkyl,C₃-C₅alkenyl, C₇-C₉aralkyl, C₅-C₇cycloalkyl, C₂-C₄hydroxyalkyl,C₂-C₆alkoxyallyl, C₆-C₁₀aryl, glycidyl or a group of the formula—(CH₂)_(p)—COO-Q or the formula —(CH₂)_(p)—O—CO-Q in which p is 1 or 2and Q is C₁-C₄alkyl or phenyl, or, if n is 2, R₃₆ is C₂-C₁₂alkylene,C₄-C₁₂alkenylene, C₆-C₁₂arylene, a group—CH₂—CH(OH)—CH₂—O-D-O—CH₂—CH(OH)—CH₂— in which D is C₂-C₁₀alkylene,C₆-C₁₅arylene or C₆-C₁₂cycloalkylene, or a group—CH₂CH(OZ′)CH₂—(OCH₂—CH(OZ′)CH₂)₂— in which Z′ is hydrogen, C₁-C₁₈alkyl,allyl, benzyl, C₂-C₁₂alkanoyl or benzoyl, T₁ and T₂ independently of oneanother are hydrogen, C₁-C₁₈alkyl or C₆-C₁₀aryl or C₇-C₉aralkyl each ofwhich is unsubstituted or substituted by halogen or C₁-C₄alkyl, or T₁and T₂, together with the C atom linking them, form a C₅-C₁₂cycloalkanering.

[0331] Examples of possible C₁-C₁₂alkyl substituents are methyl, ethyl,n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl,2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

[0332] Examples of possible C₁-C₁₈alkyl substituents can be the groupsdefined above and also, for example, n-tridecyl, n-tetradecyl,n-hexadecyl or n-octadecyl.

[0333] Examples of possible C₂-C₆alkoxyalkyl substituents aremethoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl,ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl,isopropoxyethyl or propoxypropyl.

[0334] Examples of R₃₇ as C₃-C₅alkenyl are 1-propenyl, allyl, methallyl,2-butenyl or 2-pentenyl.

[0335] As C₇-C₉aralkyl, R₃₇, T₁ and T₂ are especially phenethyl or, inparticular, benzyl. If T₁ abd T₂, together with the C atom, form acycloalkane ring, this can, for example, be a cyclopentane, cyclohexane,cyclooctane or cyclododecane ring Examples of R₃₇ as C₂-C₄hydroxyalkylare 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

[0336] As C₆-C₁₀aryl, R₃₇, T₁ and T₂ are especially phenyl, a-naphthylor p-naphthyl each of which is unsubstituted or substituted by halogenor C₁-C₄alkyl.

[0337] Examples of R₃₇ as C₂-C₁₂alkylene are ethylene, propylene,2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene,decamethylene or dodecamethylene.

[0338] As C₄-C₁₂alkenylene, R₃₇ is especially 2-butenylene,2-pentenylene or 3-hexenylene.

[0339] Examples of R₃₇ as C₆-C₁₂arylene are o-, m- or p-phenylene,1,4-naphthylene or 4,4′-biphenylene.

[0340] Examples of Z′ as C₂-C₁₂alkanoyl are propionyl, butyryl, octanoylor dodecanoyl, but preferably acetyl.

[0341] As C₂-C₁₀alkylene, C₆-C₁₅arylene or C₆-C₁₂cycloalkylene, D is asdefined under b).

[0342] The following compounds are examples of polyalkylpiperidinecompounds of this class:

[0343] 56)3-Benzyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione,

[0344] 57)3-n-Octyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4dione,

[0345] 58)3-Allyl-1,3,8-triaza-1,7,7,9,9-pentamethylspiro[4.5]decane-2,4-dione,

[0346] 59)3-Glycidyl-1,3,8-triaza-7,7,8,9,9-pentamethylspiro[4.5]decane-2,4dione,

[0347] 60)1,3,7,7,8,9,9-Heptamethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,

[0348] 61)2-Isopropyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane,

[0349] 62)2,2-Dibutyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane,

[0350] 63)2,2,4,4-Tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane,

[0351] 64)2-Butyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxospiro[4.5]decane,

[0352] 65)8-Acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione

[0353] or the compounds of the following formulae:

[0354] e) Compounds of the formula VII,

[0355] in which n is the number 1 or 2 and R₃₃ is a group of the formula

[0356] in which R and R₃₁ are as defined under a), E is —O— or —NR₄₁—, Ais C₂-C₆alkylene or —(CH₂)₃—O— and x is the numbers 0 or 1, R₃₉ isidentical with R₃₈ or is one of the groups —NR₄₁R₄₂, —OR₄₃, —NHCH₂OR₄₃or —N(CH₂OR₄₃)₂, R₄₀ is identical with R₃₈ or R₃₉, if n is 1, and, if nis 2, is a group -E-B-E- in which B is C₂-C₆alkylene which can beinterrupted by —N(R₄₁)—, R₄₁ is C₁-C₁₂alkyl, cyclohexyl, benzyl orC₁-C₄hydroxyalkyl or a group of the formula

[0357] R₄₂ is C₁-C₁₂alkyl, cyclohexyl, benzyl or C₁-C₄hydroxyalkyl andR₄₃ is hydrogen, C₁-C₁₂alkyl or phenyl or R₄₁ and R₄₂ together areC₄-C₅alkylene or C₄-C₅oxaalkylene, for example

[0358] or a group of the formula N—R₂₁

[0359] Examples of possible C₁-C₁₂alkyl substituents are methyl, ethyl,n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl,2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

[0360] Examples of possible C₁-C₄hydroxyalkyl substituents are2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl; 2-hydroxybutyl or4-hydroxybutyl.

[0361] Examples of A as C₂-C₆alkylene are ethylene, propylene,2,2-dimethylpropylene, tetramethylene or hexamethylene.

[0362] Examples of R₄ and R₄₂ together as C₄-C₅alkylene or oxaalkyleneare tetramethylene, pentamethylene or 3-oxapentamethylene.

[0363] The compounds of the following formulae are examples ofpolyalkylpiperidine compounds of this class:

[0364] f) Oligomeric or polymeric compounds in which the recurringstructural unit contains a 2,2,6,6-tetraalkylpiperidine radical of theformula (I), in particular polyesters, polyethers, polyamides,polyamines, polyurethanes, polyureas, polyaminotriazines,poly(meth)acrylates, poly(meth)acrylamides and copolymers thereofcontaining radicals of this type.

[0365] The compounds of the following formulae in which m is a numberfrom 2 to about 200 are examples of 2,2,6,6-polyalkylpiperidine lightstabilizers of this class.

[0366] Of these classes of compounds, classes a), d), e) and f) areparticularly suitable, in particular the Compounds Nos. 10, 13, 14, 23,24, 28, 29, 45, 47, 48, 63, 65, 69, 75, 77, 81, 84, 92 and 93.

[0367] Examples of organic materials which can be stabilized with themixture of (a) and (b) or with a compound of the formula Ia are fats,waxes, oils, cosmetics or photographic materials, but particularlyorganic polymers. The following classes are examples of polymers of thistype:

[0368] 1. Polymers of monoolefins and diolefins, for examplepolypropylene, polyisobutylene, polybut-1-ene, polymethylpent-1-ene,polyisoprene or polybutadiene, and polymerizates of cycloolefins, forexample cyclopentene or norbornene; and also polyethylene (which can, ifdesired, be crosslinked), for example high-density polyethylene (HDPE),low-density polyethylene (LDPE) and linear low-density polyethylene(LLDPE).

[0369] 2. Mixtures of the polymers mentioned under 1), for examplemixtures of polypropylene with polyisobutylene or of polypropylene withpolyethylene (for example PP/HDPE or PP/LDPE) and mixtures of differenttypes of polyethylene (for example LDPE/HDPE).

[0370] 3. Copolymers of monoolefins and diolefins with one another orwith other vinyl monomers, for example ethylene/propylene copolymers,linear low-density polyethylene (LLDPE) and mixtures thereof withlow-density polyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acidcopolymers and salts thereof (ionomers), and also terpolymers ofethylene with propylene and a diene, such as hexadiene,dicyclopentadiene or ethylidenenorbornene; and also mixtures of suchcopolymers with one another and with polymers mentioned under 1), forexample polypropylene/ethylene/propylene copolymers, LDPE-ethylene/vinylacetate copolymers, LDPE-ethylene/acrylic acid copolymers,LLDPE-ethylene/vinyl acetate copolymers and LLDPE-ethylene/acrylic acidcopolymers.

[0371] 3a Hydrocarbon resins (for example C₅-C₉), including hydrogenatedmodifications thereof (for example tackifying resins).

[0372] 4. Polystyrene, poly-(p-methylstyrene) andpoly-(a-methylstyrene).

[0373] 5. Copolymers of styrene or x-methylstyrene with dienes oracrylic derivatives, for example styrene/butadiene,styrene/acrylonitrile, styrene/alkyl methacrylate,styrene/butadiene/alkyl acrylate, styrene/maleic anhydride orstyrene/acrylonitrile/methyl acrylate; mixtures of high impactresistance formed from styrene copolymers and another polymer, forexample a polyacrylate, a diene polymer or an ethylene/propylene/dieneterpolymer, and block copolymers of styrene, for examplestyrene/butadiene/styrene, styrene/isoprene/styrene,styrene/ethylene-butylene/styrene or styrene/ethylene-propylene/styrene.

[0374] 6. Graft copolymers of styrene or α-methylstyrene, for examplestyrene on polybutadiene, styrene on polybutadiene/styrene orpolybutadiene/acrylonitrile copolymers, styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene, styrene and maleimide on polybutadiene, styrene andalkyl acrylates or alkyl methacrylates on polybutadiene, stytene andacrylonitrle on ethylene/propylene/diene terpolymers, styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers and mixtures thereofwith the copolymers mentioned under 5), such as are known, for example,as so-called ABS, MBS, ASA or AES polymers.

[0375] 7. Halogen-containing polymers, for example polychloroprene,chlorinated rubber, chlorinated or chlorosulfonated polyethylene,copolymers of ethylene and chlorinated ethylene, epichlorohydrinhomopolymers and copolymers, in particular polymers formed fromhalogen-containing vinyl compounds, for example polyvinyl chloride,polyvinylidene chloride, polyvinyl fluoride or polyvinylidene fluoride;and copolymers thereof, such as vinyl chloride/vinylidene chloride,vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate.

[0376] 8. Polymers derived from a,-unsaturated acids and derivativesthereof, such as polyacrylates and polymethacrylates, polyacrylamidesand polyacrylonitriles.

[0377] 9. Copolymers of the monomers mentioned under 8) with one anotheror with other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate copolymers, acrylonitrile/vinylhalide copolymers or acrylonitrile/alkyl methacrylate/butadieneterpolymers.

[0378] 10. Polymers derived from unsaturated alcohols and amines or acylderivatives or acetals thereof, such as polyvinyl alcohol, polyvinylacetate, stearate, benzoate or maleate, polyvinylbutyral, polyallylphthalate or polyallylmelamine; and copolymers thereof with olefinsmentioned in item 1.

[0379] 11. Homopolymers and copolymers of cyclic ethers, such aspolyalkylene glycols, polyethylene oxide, polypropylene oxide orcopolymers thereof with bisglycidyl ethers.

[0380] 12. Polyacetals, such as polyoxymethylene, and alsopolyoxymethylenes of this type containing comonomers, for exampleethylene oxide, and polyacetals modified with thermoplasticpolyurethanes, acrylates or MBS.

[0381] 13. Polyphenylene oxides and sulfides and mixtures thereof withstyrene polymers or polyamides.

[0382] 14. Polyurethanes derived from polyethers, polyesters andpolybutadienes having terminal hydroxyl groups on the one hand and fromaliphatic or aromatic polyisocyanates on the other hand, and alsoprecursors thereof.

[0383] 15. Polyamides and copolyamides derived from diamines anddicarboxylic acids and/or from aminocarboxylic acids or thecorresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6,6/10, 6/9, 6/12 or 4/6, polyamide 11, polyamide 12 and aromaticpolyamides formed from m-xylene, diamine and adipic acid; and polyamidesprepared from hexamethylenediamine and isophthalic and/or terephthalicacid and, if appropriate, an elastomer as modifier, for examplepoly-2,4,4-trimethylhexamethyleneterephthalamide orpoly-m-phenyleneisophthalamide. Block copolymers of the polyamidesmentioned above with polyolefins, olefin copolymers, ionomers orchemically attached or grafted elastomers; or with polyethers, forexample polyethylene glycol, polypropylene glycol or polytetramethyleneglycol. Also polyamides or copolyamides modified with EPDM or ABS; andpolyamides which have been condensed during processing (“RIM polyamidesystems”).

[0384] 16. Polyureas, polyimides, polyamide-imides andpolybenzimidazoles.

[0385] 17. Polyesters derived from dicarboxylic acids and dialcoholsand/o-r from hydroxycarboxylic acids or the corresponding lactones, suchas polyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoates andblock polyether esters derived from polyethers having hydroxyl endgroups; and also polyesters modified with polycarbonates or MBS.

[0386] 18. Polycarbonates and polyester carbonates.

[0387] 19. Polysulfones, polyether sulfones and polyether ketones.

[0388] 20. Crosslinked polymers derived from aldehydes on the one handand phenols, urea or melamine on the other hand, such asphenol/formaldehyde, urea/formaldehyde and melamine/formaldehyde resins.

[0389] 21. Drying and non-drying alkyd resins.

[0390] 22. Unsaturated polyester resins derived from copolyesters ofsaturated and unsaturated dicarboxylic acids with polyhydric alcohols,and also vinyl compounds as crosslinking agents, and alsohalogen-containing modifications thereof of low flammability.

[0391] 23. Crosslinkable acrylic resins derived from substituted acrylicacid esters, for example from epoxyacrylates, urethane acrylates orpolyester acrylates.

[0392] 24. Alkyd resins, polyester resins and acrylate resinscrosslinked with melamine resins, urea resins, polyisocyanates or epoxyresins.

[0393] 25. Crosslinked epoxy resins derived from polyepoxides, forexample from bis-glycidyl ethers or cycloaliphatic diepoxides.

[0394] 26. Natural polymers, such as cellulose, natural rubber, gelatineand the polymer-homologously chemically modified derivatives thereof,such as cellulose acetates, propionates and butyrates or the celluloseethers, such as methylcellulose; and also colophony resins andderivatives.

[0395] The use of the compounds according to the invention in coatingsof all types is particularly preferred. These can be pigmented orunpigmented coatings or metal effect coatings. They can contain anorganic solvent or can be solvent-free or can be aqueous coatings.

[0396] The coatings can contain, as a binder, at least one of thepolymers listed above. The following are examples of coatings containingspecial binders:

[0397] 1. Coatings based on cold-crosslinkable or hot-crosslinkablealkyd, acrylate, polyester, epoxy or melamine resins or mixtures of suchresins, if desired with an added acid curing catalyst;

[0398] 2. Two-component polyurethane coatings based on acrylate,polyester or polyether resins containing hydroxyl groups, and onaliphatic or aromatic polyisocyanates;

[0399] 3. One-component polyurethane coatings based on maskedpolyisocyanates which are unmasked during baking;

[0400] 4. Two-component coatings based on (poly)ketimines and aliphaticor aromatic polyisocyanates;

[0401] 5. Two-component coatings based on (poly)ketimines and anunsaturated acrylate resin or a polyacetoacetate resin or a methylmethacrylamidoglycolate;

[0402] 6. Two-component coatings based on polyacrylates and polyepoxidescontaining carboxyl or amino groups;

[0403] 7. Two-component coatings based on acrylate resins containinganhydride groups, and on a polyhydroxyl or polyamino component;

[0404] 8. Two-component coatings based on (poly)oxazolidines andacrylate resins containing anhydride groups, or unsaturated acrylateresins or aliphatic or aromatic polyisocyanates;

[0405] 9. Two-component coatings based on unsaturated polyacrylates andpolymalonates;

[0406] 10. Thermoplastic polyacrylate coatings, based on thermoplasticacrylate resins or extraneously crosslinking acrylate resins incombination with etherified melamine resins;

[0407] 11. Coating systems based on siloxane-modified or silane-modifiedor fluorine-modified acrylate resins.

[0408] The coatings can also be radiation-curable. In this case thebinder is composed of monomeric or oligomeric compounds which containethylenic double bonds and are converted into a crosslinked,high-molecular form by irradiation with actinic light or with electronbeams. In most cases the binder is a mixture of such compounds. Inradiation-curable coatings the compounds of formula I can be used alsoin absence of a sterically hindered amine.

[0409] The coatings can be applied as one-coat or two-coat systems, itbeing preferable to add the stabilizers according to the invention tothe unpigmented top coat.

[0410] The coatings can be applied to the substrates (metal, plastic,wood, etc.) by the customary processes, for example by brushing,spraying, curtain-coating, dipping or electrophoresis.

[0411] The amount of (a) and (b) added depends on the substrate and therequirements for its stability. In general, 0.01 to 5% by weight, inparticular 0.02 to 2% by weight, of the component (a) and 0.02 to 5% byweight, in particular 0.05 to 3% by weight, of the component (b) areadded, relative to the polymer.

[0412] The two components can be added on their own or as a mixture.Addition is preferably carried out before or during the shaping of thepolymer. It can also be carried out as early as the preparation of thepolymer, for example before or during polymerization.

[0413] The compounds of the formula Ia can also be used on their own,ie. without a sterically hindered amine, for stabilizing organicpolymers. In this case 0.01 to 10% by weight, for example, preferably0.05 to 5% by weight, of a compound of the formula Ia is added to thepolymer. The use of compounds of the formula Ia as a stabilizer forpolycarbonates is of particular interest.

[0414] In addition to the stabilizers, according to the invention, ofthe formula Ia or the stabilizer combination (a)+(b), it is alsopossible to add other stabilizers to the polymer. The following areexamples of these:

[0415] 1. Antioxidants

[0416] 1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-di-cyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol and 2,6-di-nonyl-4-methylphenol.

[0417] 1.2. Alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone and 2,6-diphenyl-4-octadecyloxyphenol.

[0418] 1.3. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis-(6-tert-butyl-4-methylphenol),2,2′-thiobis-(4-octylphenol),4,4′-thiobis-(6-tert-butyl-3-methylphenol),4,4′-thiobis-(6-tert-butyl-2-methylphenol).

[0419] 1.4. Alkylidene bisphenols, for example2,2′-methylenebis-(6-tert-butyl-4-methylphenol),2,2′-methylenebis-(6-tert-butyl-4-ethylphenol),2,2′-methylenebis-[4-methyl-6-(α-methylcyclohexyl)-phenol],2,2′-methylenebis-(4-methyl-6-cyclohexylphenol),2,2′-methylenebis-(6-nonyl-4-methylphenol),2,2′-methylenebis-(4,&di-tert-butylphenol),2,2′-ethylidenebis-(4,6-di-tert-butylphenol),2,2′-ethylidenebis-(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis-[6-α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis-[6-(a ,C-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis-(2,6-di-tert-butylphenol),4,4′-methylenebis-(6-tert-butyl-2-methylphenol),1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane,2,6-bis-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane,1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis-[3,3-bis-(3′-tert-butyl-4′-hydroxyphenyl)-butyrate],bis-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene andbis-[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate.

[0420] 1.5. Benzyl compounds, for example1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,bis-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,bis:(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-dithiol terephthalate,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate,1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate,dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, the Ca salt ofmoroethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and1,3,5-tris-(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

[0421] 1.6. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide,2,4-bis-(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyaniline)-s-triazineand octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate.

[0422] 1.7. Esters of D-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionicacid, with monohydric or polyhydric alcohols, for example methanol,octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol,diethylene glycol, triethylene glycol, pentacrythritol,tris-(hydroxyethyl) isocyanurate and N,N′-bis-(hydroxyethyl)oxamide.

[0423] 1.8. Esters ofo-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydricor polyhydric alcohols, for example methanol, octadecanol,1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris-(hydroxyethyl)isocyanurate and N,N′-bis-(hydroxyethyl)oxamide.

[0424] 1.9. Esters of 5-(3,5-dicyclohexyl-4-hydroxyphenyl)-propionicacid with monohydric or polyhydric alcohols, for example methanol,octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol,diethylene glycol, triethylene glycol, pentaerythritol,tris-(hydroxyethyl) isocyanurate and N,N′-bis-(hydroxyethyl)oxamide.

[0425] 1.10. Amides of p-(35-di-tert-but yl-4-hydroxyphenyl)-propionicacid, for exampleN,N′-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine,N,N′-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamineand N,N′-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine.

[0426] 2. UV Absorbers and Light Stabilizers

[0427] 2.1. 2-(2′-hydroxyphenyl)-benzotriazoles, for example the5′-methyl-, 3′,5′-di-tert-butyl-, 5′-tert-butyl-,5′-(1,1,3,3-tetramethylbutyl)-, 5-chloro-3′,5′-di-tert-butyl-,5-chloro-3′-tert-butyl-5′-methyl-, 3′-sec-butyl-5′-tert-butyl-,4′-octoxy-, 3′,5′-di-tert-amyl-,3′,5′-bis-(α,α-dimethylbenzyl)-derivative.

[0428] 2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy-,4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-,4,2′,4′-trihydroxy- or 2′-hydroxy-4,4′-dimethoxy-derivative.

[0429] 2.3. Esters of unsubstituted or substituted benzoic acids, forexample 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol,benzoylresorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl3,5-1-tert-butyl-4-hydroxybenzoate.

[0430] 2.4. Acrylates, for example ethyl or isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl orbutyl α-cyano-β-methyl-p-methoxycinnamate, methylα-carbomethoxy-p-methoxycinnamate orN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

[0431] 2.5. Nickel compounds, for example nickel complexes of2,2′-thiobis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1complex or the 1:2 complex, if appropriate with additional ligands, suchas n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of monoalkyl4-hydroxy-3,5-di-tert-butylbenzylphosphonates, such as the methyl orethyl ester, nickel complexes of ketoximes, such as2-hydroxy-4-methylphenyl undecyl ketoxime, or nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, if appropriate with additionalligands.

[0432] 2.6. Oxamides, for example 4,4′-di-octyloxyoxanilide,2,2′-di-octyloxy-5,5′-di-tert-butyloxanilide,2,2′-di-dodecyloxy-5,5′-di-tert-butyloxanilide,2-ethoxy-2′-ethyloxanilide, N,N′-bis-(3-dimethylaminopropyl)-oxalamide,2-ethoxy-5-tert-butyl-2′-ethyloxanilide and a mixture thereof with2-ethoxy-2′-ethyl-5,4′-di-tert-butyloxanilide or mixtures of o-methoxy-and p-methoxy-disubstituted oxanilides and of o-ethoxy- andp-ethoxy-disubstituted oxanilides.

[0433] 3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloylhydrazine, N,N′-bis-(salicyloyl)-hydrazine,N,N′-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine,3-salicyloylamino-1,2,4-triazole and bis-(benzylidene)-oxalic aciddihydrazide.

[0434] 4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris-(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl) phosphite,diisodecyl pentaerythritol diphosphite, bis-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite,tetrakis-(2,4-di-tert-butylphenyl) 4,4′-biphenylene diphosphonite and3,9-bis-(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane.

[0435] 5. Compounds which destroy peroxides, for example esters ofβ-thiodipropionic acid, for example the lauryl, stearyl, myristyl ortridecyl esters, mercaptobenzimidazole, the zinc salt of2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyldisulfide and pentaerythritol tetrakis-(β-dodecylmercapto)propionate.

[0436] 6. Polyamide stabilizers, for example copper salts in combinationwith iodides and/or phosphorus compounds and salts of divalentmanganese.

[0437] 7. Basic co-stabilizers, for example melamine,polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, ureaderivatives, hydrazine derivatives, amines, polyamides, polyurethanes,alkali and alkaline earth salts of higher fatty acids, for example Castearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate,antimony pyrocatecholate or tin pyrocatecholate.

[0438] 8. PVC stabilizers, for example organotin compounds or salts ofbarium, cadmium, zinc and led.

[0439] Other materials such as are customary in the technology ofplastics and paints can also be added. Examples of these are fillers andreinforcing agents, pigments, dyes, plasticizers, solvents, lubricants,flow-control agents, fluorescent brighteners, nucleating agents,antistatic agents or fire-retarding agents.

[0440] The invention also relates, therefore, to organic polymerscontaining, as stabilizers, a sterically hindered amine of thepolyalkylpiperidine type and a hydroxyphenyltriazine of the formula I,and also to organic polymers containing a compound of the formula Ia asthe stabilizer.

[0441] The polymers stabilized in this manner can be used in variousshapes, for example as films, fibres, tapes, mouldings, profiles, latex,dispersions, paints or cements.

[0442] The following examples illustrate the invention in greater detailwithout intending to limit it to the examples. Parts and percentages areparts by weight and percentages by weight.

PREPARATION EXAMPLES Example 1

[0443] 23.8 g (0.06 mol) of2-(2,4-dihydroxyphenyl)-4,6bis-(2,4-dimethylphenyl) 1,3,5-triazine(prepared as described in U.S. Pat. No. 3,244,708 Example 16) aresuspended in 300 ml of xylene. 12.1 g (0.09 mol) of 97% butyl glycidylether and 0.75 g (0.006 mol) of dimethylbenzylamine are added to thissuspension, and the mixture is heated to reflux temperature. After areaction time of S hours the clear, brownish solution is cooled andclarified by filtration through 100 g of silica gel. The yellow solutionis evaporated and the residue is recrystallized from hexane/toluene.This gives 27.3 g of pale yellow crystals of2-[2-hydroxy-4(3-butoxy-2-hydroxypropyloxy)-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin(=86% yield). Melting point: 80-83° C. (Compound 1).

[0444] In analogous manner the compounds 2 to 28, listed in Table 1, areobtained from2-(2,4-dihydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine andan epoxy compound. TABLE 1

Compound n R₇ Physical data 1 1 —CH₂CH(OH)CH₂OC₄H₉ m.p. 80-83° C. 2 1—CH₂CH(OH)CH₂OCOC(CH₃)═CH₂ m.p. 100-103° C. 3 2—CH₂CH(OH)CH₂O—(CH₂)₄—OCH₂CH(OH)CH₂— mp. 150-152° C. 4 1

m.p. 115-117° C. 5 1 —CH₂CH(OH)CH₂—OH m.p. 165-167° C. 6 1

m.p. 101-104° C. 7 1

m.p. 75-77° C. 8 1

Oil found: C: 75.6% H: 9.2%  calc.: C: 75.9% H: 9.1% 9 2

m.p. 100-103° C. 10 1 —CH₂CH(OH)(CH₂)₁₁CH₃ m.p. 102-104° C. 11 1—CH₂CH(OH)(CH₂)₇CH₃ m.p. 97-99° C. 12 1

Oil found: C: 64.9% H: 7.6% N: 4.4%  calc.: C: 66.7% H: 7.16% N: 5.4% 131

Oil found: N: 3.75% calc.: N: 3.43% 14 2

Oil found: N: 5.17% calc.: N: 5.18% 15 1 —CH₂CH(OH)CH₂OCOC₉H₁₉ Oilfound: N: 6.3% calc.: N: 6.7% 16 1

m.p. 152-155° C. 17 1 —CH₂CH(OH)CH₂O(C₁₃H₂₇ to C₁₅H₃₁) Oil MS, NMR 18 1—CH₂CH(OH)CH₂O(C₁₂H₂₅ to C₁₄H₂₉) Oil MS, NMR 19 2

Resin found: C = 71.3%, H = 6.6% calc.: C = 71.4%, H = 6.6% 20 1—CH₂CH(OH)CH₂OCOC₁₀H₂₁-tert. Resin MS, NMR 21 1 —CH₂CH(OH)CH₂OCH₂CH═CH₂m.p. 94-95° C. 22 1 —CH₂CH(OH)CH₃ m.p. 151-153° C. 23 1

m.p. 99-101° C. 24 2

Resin found: N = 8.2% calc.: N = 8.3%

Example 2

[0445] 22.1 g (0.05 mol) of2-(2-hydroxy-4-hydroxyethoxy-phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine(prepared as described in U.S. Pat. No. 3,244,708, Example 18), aredissolved in 300 ml of tetrahydrofurane at 40° C. and 21 ml (0.15 mol)of triethylamine are added. A solution of 5.05 ml (0.053 mol) of acrylicacid chloride in 20 ml THF is added dropwise with stirring and withcooling the reaction mixture to 25-30° C. After further stirring of twohours the precipitated ammonium salt is filtered off, the filtrate isevaporated and the residue recrystallized from toluene-hexane mixture toobtain 22 g (88.7% yield) of2-(2-hydroxy-4-acryloyloxyethoxy-phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazineas slightly yellow crystals (compound No. 25),

[0446] m.p. 128-129° C.

[0447] In analogous manner the compounds No. 26 and 27 were prepared.Compound n R₇ Phys. data 25 1 —CH₂CH₂OCOCH═CH₂ m.p. 128-129° C. 26 1—CH₂CH(CH₃)OCOCH═CH₂ m.p. 128-129° C. 27 1 —CH₂CH₂OCOCH(CH₃)═CH₂ m.p.128-129° C.

Example 3

[0448] 20 g (0.04 mol) of2-(2-hydroxy-4-ethoxycarbonylmethoxyphenyl)-4,6-bis--(2,4-dimethylphenyl)-1,3,5-triazine(prepared as described in U.S. Pat. No. 3,244,708, Example 19), aredissolved in 100 ml of toluene, and 5 g (0.048 mol) of 2-methylpentanoland 0.5 g of dibutyltin oxide as catalyst are added, and the mixture isheated to reflux temperature. In the course of this a toluene/ethanolmixture is distilled off. The toluene is replenished dropwise from adropping funnel. The transesterification reaction is complete after 2hours. The solution is cooled and filtered through 80 g of silica geland is then evaporated. The residue is recrystallized from ethanol. Thisgives 14 g of the compound 28 (see Table 2). Melting point: 87-89° C.

[0449] Compounds 29 to 37 are obtained analogously bytransesterification with the corresponding alcohols. TABLE 2

Compound R₈ Physical data 28

m.p. 87-89° C. 29 —CH₂CH₂CH₂CH₃ m.p. 136-138° C. 30—C₈H_(17 (isomer mixture)) Waxlike calcd. C 74.05% H 7.28% N 7.4% foundC 73.98% H 7.36% N 7.3% 31

Oil calcd. found  C 64.47% C 64.75%  H 6.99% H 7.00%  N 5.50% N 5.72% 32—C₁₀H₂₁ (isomer mixture) Waxlike calcd. C 74.59% H 7.61% N 7.05% found C74.76% H 7.73% N 6.89% 33

Resin calcd. found  C 70.45% C 70.12%  H 7.06% H 7.02%  N 6.85% N 6.84%34

m.p. 75-78° C. 35 —(CH₂)₈CH═CH(CH₂)₇—CH₃ Waxlike calcd. C 76.96% H 8.42%N 5.95% found C 77.02% H 8.47% N 5.74% 36 —(CH₂)₂O(CH₂)₂OC₆H₁₃ Resincalcd. C 70.68% H 7.37% N 6.68% found C 70.53% H 7.49% N 6.39% 37

Resin calcd. found  C 63.44% C 63.54%  H 7.22% H 7.20%  N 4.93% N 5.01%

Example 4

[0450] 9.1 g (0.02 mol) of2-(2-hydroxy-4-carboxymethoxy-phenyl)-4,67bis(2,4-dimethylphenyl)-1,3,5-triazine(prepared as described in U.S. Pat. No. 3,244,708, Example 16) aresuspended in 40 ml of thionyl chloride, and 1 ml of DMF is added. Themixture is heated at reflux temperature for 2 hours. A clear yellowsolution is formed with moderate evolution of gas. This solution isevaporated to give 9.5 g of[4-(4,6-di-2′,4′-xylyl-s-triazin-2-yl)₃-hydroxyphenoxy]-acetyl chloride(Compound 38). This acid chloride is dissolved in 100 ml of toluene.19.3 g (0.08 mol) of bis-(2-ethylhexyl)-amine are added dropwise at roomtemperature. The reaction proceeds exothermically from 22° C.

[0451] to 40° C. The mixture is left for 1 hour at room temperature tocomplete the reaction. The product is then purified by columnchromatography over silica gel. This gives approx. 5 g of a pale yellow,highly viscous oil,[4-(4,6-di-2′,4′-xylyl-s-trazin-2-yl)-3-hydroxyphenoxy]-acetic acidbis-(2-ethylhexyl)-amide (Compound 39).

[0452] Calcd. C 76.07%, H 8.61%, N 8.25%

[0453] Found. C 75.91%, H 8.46%, N 8.16%

Example 5

[0454] 39.7 g (0.1 mol) of2-(2,4-dihydroxyphenyl)-4,bis(2,4-dimethylphenyl) 1,3,5-triazine aredissolved in 250 ml of DMF. 20.7 g of potassium carbonate are added tothis brownish solution. An orange suspension is formed. 17 g (0.052 mol)of 1,12-di-bromododecane are added and the mixture is heated at 100° C.The reaction is complete after 2 hours. The cooled reaction solution isthen poured into 1.5 l of water, and the precipitate is filtered off andwashed with 2-3 times 100-200 ml of H₂O. The crystals are thenrecrystallized from xylene. Melting point: 158-163° C. (Compound 40).

[0455] Compounds 41 and 42 are obtained analogously, using1,6-dibromohexane, 1,4-dichloro-2-butene and p-xylylenedibromid. TABLE 3

Compound R₇ Physical data 40 —(CH₂)₁₂— m.p. 158-163° C. 41 —(CH₂)₆— m.p.203-205° C. 42 —CH₂CH═CH—CH₂— m.p. 230-235° C. 43

m.p. 252-254° C.

Example 6

[0456]20 g (0.05 mol) of2-(2,4dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine aresuspended in 100 ml of toluene, and 100 ml of 1N NaOH and 1 g oftetrabutylammonium bromide are added. The mixture is heated for 10minutes at 80° C. and then cooled, to give a yellow paste. 12.3 ml (0.15mol) of epibromohydrin are added to this paste and the mixture is againheated for 6 hours at 50° C. When the reaction is complete, methylenechloride is added to the organic phase, which is separated off from theaqueous phase and filtered through Hyflo. It is then evaporated and thecrystalline residue is recrystallized from toluene. This gives 14 g ofpale yellow crystals,2-(2-hydroxy-4-glycidyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine(Compound 44), melting point 152-155° C.

Example 7

[0457] 9.07 g (0.02 mol) of Compound 44 and 7.95 g (0.02 mol) of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine aresuspended in 150 ml of xylene. 0.2 g of dimethylaminopyridine are addedand the mixture is heated at reflux temperature. The reaction iscomplete after 4 hours. The mixture is diluted with 200 ml of tolueneand cooled. In the course of this the product is precipitated. It isfiltered off and purified further by recrystallization from toluenetogether with a little Fuller's earth. This gives 9.1 g of pale beigecrystals,1,3-bis-(4-[4,6-di-(2,4-dimethylphenyl)-s-triazine-2-yl]-3-hydroxy-phenoxy)-2-hydroxypropane(Compound 45), melting point: 222-224° C.

Example 8

[0458] 18.5 g (0.05 mol) of2-(2,4-dihydroxyphenyl)-4,6-bis-(4-methylphenyl)-1,3,5-triazine (Helv.Chim. Acta 55, 1566 (1972)) and 3.9 g (0.05 mol) of potassium methoxideare suspended in 200 ml of anhydrous n-butanol, and 7.4 g (0.06 mol) ofbutyl chloroacetate are added dropwise between 50° C. and 100° C. After17 hours under reflux the solvent is evaporated and the crude product iswashed with water, dried and recrystallized from petroleum ether(boiling point 110° C.-140° C.) (Compound No. 46).

[0459] Melting point: 142-146° C.

[0460] Calcd. C 72.03H 6.04 N 8.69%

[0461] Found C 71.88H 6.01 N 8.81%

Example 9

[0462] A) 55.4 g (0.15 mol) of2-(2,4-dihydroxyphenyl)-4,6-bis-(4-methylphenyl)-1,3,5-triazine aredissolved in refluxing 2-butanone (1 l) in the presence of 27.6 g (0.2mol) of K₂CO₃. A catalytic amount (0.2 g) of KI is added, and 36.8 g(0.3 mol) of ethyl chloroacetate are-added dropwise over 1 h30. Afterrefluxing for 25 h, the reaction mixture is cooled in ice, theprecipitate is filtered off, washed with water to neutrality and thenwith methanol. Drying in the oven yields the analytically pure2-(2-hydroxy-4-ethoxycarbonylmethoxyphenyl)-4,6-bis-(4-methylphenyl)-1,3,5-triazine(54 g, m.p. 166167° C.) (Compound No. 47).

[0463] B) 11.4 g (0.025 mol) of compound 47 and 3.9 g (0.03 mol) ofoctanol (isomeric mixture) are refluxed in 120 ml xylene for 22 h in thepresence of 0.62 g (2.5 mmol) of dibutyltinoxide. During the reaction axylene/ethanol mixture is distilled off, the xylene being replenisheddropwise from a dropping funnel. The reaction mixture is cooled to 40°C., filtered through a pad of Prolith and evaporated. Drying at 100°C./0.01 mmHg affords the transesterification product as a viscous yellowoil (12.5 g) that solidifies to a wax (Compound No. 48).

[0464] Calcd. C=73.44%,H=6.91%, N=7.79%

[0465] Found C=72.95%, H=6.70%, N=7.48%

[0466] Compounds No. 49 to 52 (Table 4) are obtained analogously bytransesterification with the corresponding alcohols. TABLE 4

Compound n R₇ Physical data 49 1 —CH₂CH₂OCH₃ m.p. 150-153° C. 50 2—CH₂CH₂OCH₂CH₂OC₂H₅ m.p. 118-121° C. 51 2 —(CH₂)₆— m.p. 235-238° C. 52 4

m.p. 219-231° C.

Example 10

[0467] 40.6 g (0.11 mol) of2-(2,4-dihydroxyphenyl)4,6-bis-(4-methylphenyl)-1,3,5-triazine aredissolved in refluxing 2-butanone (500 ml) in the presence of 20.7 g(0.15 mol) of K₂CO₃. 18.1 g (0.055 mol) of 1,12-dibromodecane dissolvedin 100 ml of 2-butanone are added dropwise over 3 h and the mixture isrefluxed for 35 h. In the course of this, precipitation of the finalproduct occurs. The reaction mixture is cooled in ice, the precipitateis filtered off, washed with water to neutrality and then with methanol.Drying in the oven affords 46.2 g of the analytically pure compound No.53 (Table 5,. Off-white solid, m.p. 219-220° C.

[0468] Analogous treatment with 1,6-dibromohexane or epibromohydringives compounds No. 54 and 55 (Table 5). TABLE 5

Compound n R₇ Physical data 53 2 —(CH₂)₁₂— m.p. 219-220° C. 54 2—(CH₂)₆— m.p. 247-249° C. 55 1

m.p. 205-208° C. 56 1

m.p. 166-167° C. 57 1

m.p. 123-125° C. 58 1

Yellow oil calc. C 66.02% H  6.89% N  5.63%  found 64.52%  6.98%  5.23%59 1

m.p. 183-185° C. 60 1

m.p. 135-138° C. 61 2 —OC—(CH₂)₈—CO— m.p. 220-228° C.

Example 11

[0469] A mixture of 14.8 g (0.04 mol) of2-(2,4-dihydroxyphenyl)4,6-bis-(4-methylphenyl)-1,3,5-triazine, 10.4 g(0.08 mol) of butylglycidylether and 2.1 g (6.5 mmol) oftetrabutylammoniumbromide is refluxed in 150 ml of 2-butanone during 85h. The reaction mixture is cooled in ice, the precipitate is filteredoff, washed with water and methanol, and dried in the oven. This yields17.5 g of a pale yellow solid, m.p. 166167° C. (Compound No. 56, Table4).

[0470] Analogous treatment with the corresponding glycidyl ethers oresters yields the compounds 57 to 60 (Table 4).

Example 12

[0471] A solution of 3.6 g (0.015 mol) of sebacyl chloride in 10 mltoluene is added dropwise at 10° C. to a solution of2-(2,4-dihydroxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine and 3.3 g(0.033 mol) of triethylamine in 100 ml toluene and 50 ml of DMF. After50 h at room temperature, the reaction mixture is diluted with water,filtered, the precipitate is washed with water, methanol and chloroform,and dried in the oven. 8.7 g of the diester 61 (Table 4) are obtained asa pale beige solid, m.p. 220-228° C.

Example 13

[0472] When 20.5 g (0.06 mol) of2-(2,4-hydroxyphenyl)-4,6-diphenyl-1,3,5-triazine are treated with 22.8g (0.12 mol) of 2-ethylhexyl glycidyl ether analogously to example 11,23.3 g of the pale yellow compound No. 62 (m.p. 116 to 118° C.) areobtained.

Example 14

[0473] 7.9 g (0.02 mol) of2-(2,4-dihydroxyphenyl)4,6-bis(2,4-dimethylphenyl) 1,3,5-triazine, 5.7 g(0.02 mol) of a technical mixture of dodecyl, tridecyl and tetradecylglycidyl ethers (Araldite® DY 025) and 0.15 g of ethyltriphenylphosphonium iodide in 50 ml of mesitylene are heated at160-165° C. for 10 hours, with stirring. The reaction solution is washedwith water, dried over MgSO₄ and filtered. The filtrate is stirred for 2hours with 2 g of Filtrol 4, filtered and evaporated in vacuo. Theresidue is freed from residual mesitylene at 120° C. and 0.01 mmHg. Thisleaves 12.1 g of an oil (Compound No. 63). C₄₁H₃₅N₃O₄ Calcd. C 75.30 H8.48 N 6.43% Found. C 75.0  H 8.1  N 6.8% 

APPLICATION EXAMPLES Example 15 Stabilization of a 2-Coat MetallicCoating

[0474] A clear lacquer is prepared by mixing the following components:59.2 Parts of a commercial acrylic resin (Uracon ® XB 2263, DMS ResinsBV, NL) which is a 50% solution in xylene. 11.6 parts of a 90% melamineresin (Cymel ® 327, Amer. Cyanamid Corp.) 19.4 parts of xylene 5.5 partsof butylgylcol acetate 9.3 parts of butanol 1.0 part of a leveling agent(Baysilon ® A, Bayer AG) which is a 1% solution in xylene

[0475] Samples of this laquer are mixed with 0.5% (related to thesolids) of di(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate (═HA-1) and1,5% (related to the solids) of a triazine stabilizer listed in table 6.

[0476] The clear lacquer is diluted to a sprayable state with a mixtureof 13:6:1 xylene/butanol/butyl glycol acetate and is sprayed onto apreviously prepared aluminum sheet (coil-coated and primed with-asilver-metallic paint based on polyester/celluloseacetobutyrate/melamine resin), and the sheet is baked for 30 minutes at130° C. This results in a dry film thickness of 40-50 μm of clearlacquer. A clear lacquer containing no light stabilizer is used as acomparison.

[0477] The samples are exposed in a UVCON, Type UVB-313, weatheringequipment with a cycle of 8 hrs of dry UV irradiation at 70° C. and 4hrs of condensation at 50° C. The 200-gloss of the samples is measuredin certain intervals of weathering time using the method of DIN 67530.The results are given in Table 6. TABLE 6 Piperidin Triazine Stabilizer20°-Gloss after exposure of Stabilizer (Compound No.) 0 1600 3200 48006400 hrs — — 86 31 — — — 0.5% HA-1 1.5%  1 86 79 74 77 61 0.5% HA-11.5% 30 86 74 68 66 57 0.5% HA-1 1.5% 32 82 69 72 68 59 0.5% HA-11.5% 33 85 79 74 72 64

Example 16

[0478] The preparation of the samples and their testing is the same asin Example 15. As comparison C—I and C-2, two triazine derivatives knownfrom U.S. Pat. No. 4,619,956, are used as triazine stabilizers.

[0479] C-1=2-(2-hydroxy-4-dodecyloxyphenyl)-46-diphenyl-1,3,5-triazine

[0480] C-2=2-(2-hydroxy-4-octadecyloxyphenyl)-4,6diphenyl-1,3,5-triazine

[0481] The results are shown in Table 7. TABLE 7 Piperidin 20°-Glossafter exposure of Stabilizer Triazine Stabilizer 0 1600 3200 4000 hrs —— 84 19 — — 0.5% HA-1 1.5% Compound 34 84 80 78 59 0.5% HA-1 1.5%Compound 35 85 81 80 75 0.5% HA-1 1.5% Compound 36 85 80 78 76 0.5% HA-11.5% Compound 37 85 80 79 77 0.5% HA-1 1.5% Compound 39 85 81 72 74 0.5%HA-1 1.5% C-1 85 54 35 37 0.5% HA-1 1.5% C-2 79 38 34 37

Example 17

[0482] A similar clear lacquer is prepared from 54.5 parts of Uracon ®XB 2263 16.3 parts of Cymel ® 327 19.4 parts of xylene 5.5 parts ofbutylgylcol acetate 3.3 parts of butanol 1 part of Baysilon ® A

[0483] Samples of this laquer are mixed with 0.5% (related to thesolids) of HA-1 and 1.5% (related to the solids) of a triazinestabilizer listed in Table 8. The lacquer is diluted to a sprayablestate by diluting with a 13:6:1 mixture of xylene/butanol/butylglycolacetate and is sprayed onto an aluminium sheet which is coil coated andprimed with a metallic blue commercial paint (Glasomax®. Glasurit GmbH,Münster). After baking for 30 minutes at 130° C. the clear lacquer layerhas a thickness of 40-45 μm.

[0484] The samples are weathered in a UVCON, Type UVB 313, as describedin Example 15 and the 20′-gloss of the weathered samples is measuredaccording to method DIN 67530. The results are shown in Table 8. TABLE 8Piperidin Triazine Stabilizer 20°-Gloss after exposure Stabilizer(Compound No.) 0 800 1600 2000 hrs — — 85 75 42 20 0.5% HA-1 1.5%  4 8680 78 78 0.5% HA-1 1.5%  6 87 81 81 81 0.5% HA-1 1.5%  7 85 81 81 790.5% HA-1 1.5% 10 86 82 80 80 0.5% HA-1 1.5% 11 86 81 81 78 0.5% HA-11.5% 17 86 81 81 81 0.5% HA-1 1.5% 18 87 81 80 80 0.5% HA-1 1.5% 62 8480 78 81

Example 18

[0485] The two-coat samples are prepared as described in Example 15,however, no piperidin stabilizer is added The samples are weathered in aWeatherometer with cycle CAM 159 and with using an edge filter of typeA. Measured is the 20′-gloss before and after exposure, the results areshown in Table 9. TABLE 9 Triazine Stabilizer 20°-Gloss after exposureof (Compound No.) 0 2000 3600 hrs none 85 47 25 34 86 71 64 35 86 72 6136 86 73 60

Example 19

[0486] The two-coat samples are prepared as described in Example 17,however, no piperidin stabilizer is added. The samples are weathered ina UVCON, type UVB-313 with cycle of 8 hrs of UV irradiation at 70° C.and 4 hrs of condensation at 50° C. The 20′-gloss of the sample ismeasured according to method DIN 67530 before and after exposure.Further the change of colour shade AE after exposure is measuredaccording to method DIN 6174. The results are shown in Table 10. TABLE10 20°-Gloss after Triazine Stabilizer exposure of ΔE (Compound No.) 0800 1600 hrs after 1600 h none 85 75 42 6.6  6 84 80 80 1.3  7 84 81 801.3 17 86 81 80 1.6 18 86 81 80 1.4 62 86 82 81 1.0

Example 20 Stabilization of a Radiation-Curable System

[0487] A clear laquer is prepared by mixing 14 parts oftris(2-acryloyloxyethyl)isocyanurate with 6 parts of 1,6-hexanedioldiacrylate and 0.4 parts of 1-benzoylcyclohexanol (as photoinitiator). Atrazine stabilizer is added in an amount of 1.5%. The lacquer is coatedto a white coil-coated aluminium sheet in a dry-thickness of about 40μm.

[0488] The samples are hardened by UV irradiation in a PPG processor(2×80 W/cm, 2×10 m (min) and weathered in a UVCON, type UVB-313 with acycle of 4 hours of UV irradiation at 60° C. and 4 hrs of condensationat 50° C.

[0489] The yellowness index (method ASTM D 1925-70) of the samples ismeasured before and after the exposure. The results are shown in Table11. TABLE 11 Triazine Stabilizer Yellowness Index after exposure of(Compound No.) 0 200 400 600 hrs none −1.0 19.6 28.0 35.3 1.5% 17 −0.61.8 1.8 2.1

What is claimed is:
 1. An organic material which has been stabilized against damage caused by light, heat and oxygen and which contains (a) at least one sterically hindered amine of the polyalkylpiperidine type and (b) at least one o-hydroxyphenyl-s-triazine, wherein the triazine compound (b) is a compound of the formula I

in which n is 1 to 4, R₁ and R₂ independently of one another are H, OH, C₁-C₁₂alkyl, cyclohexyl or trifluoromethyl, R₃ and R₄ independently of one another are H, OH, C₁-C₁₂alkyl, cyclohexyl, C₁-C₁₈alkoxy or halogen and, in the event that n=1, can also be a radical —OR₇, R₅ and R₆ independently of one another are H. C₁-C₁₂alkyl or halogen, R₇, if n is 1, is a) C₁-C₁₈alkyl which is substituted by one or more of the groups OH, C₁-C₁₈alkoxy, C₃-C₁₈alkenoxy, halogen, phenoxy (which is unsubstituted or substituted by C₁-C₁₈alkyl, C₁-C₁₈alkoxy or halogen), furyloxy,

 —COOH, —COOR₉, —CONH₂, —CONHR₉, —CON(R₉)(R₁₀), —NH₂, —NH₉, —N(R₉)(R₁₀), —NHCOR₁₁, —CN and/or by —O—CO—R₁₁, b) C₄-C₅₀alkyl which is interrupted by one or more O and can be substituted by OH or/and glycidyloxy, c) C₃-C₆alkenyl, d) glycidyl or a group

e) cyclohexyl which is unsubstituted or substituted by OH or —OCOR₁, f) C₇-C₁₁phenylalkyl which is unsubstituted or substituted by OH, Cl or CH₃, g) —CO—R₁₂ or h) —SO₂—R₁₃, and if n is 2, R₇ is a) C₂-C₁₆alkylene, b) C₄-C₁₂alkenylene, c) xylylene, d) C₃-C₂₀alkylene which is interrupted by one or more O and/or substituted by OH, e) a group —CH₂CH(OH)CH₂O—R₁₅—OCH₂CH(OH)CH₂—, —CO—R₁₆—CO—, —CO—NH—R₁₇—NH—CO— or —(CH₂)_(m)—COO—R₁₈—OOC—(CH₂)_(m)— (in which m is 1 to 3) or

and if n is 3, R₇ is a group

and if n is 4, R₇ is a group

R₈ is C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₂₀alkyl which is interrupted by one or more O, N or S and/or substituted by OH, C₁-C₄alkyl which is substituted by —P(O)(OR₁₄)₂, —N(R₉)(R₁₀) or —OCOR₁₁ and/or OH, C₃-C₁₈alkenyl, glycidyl or C₇-C₁₁phenylalkyl, R₉ and R₁₀ independently of one another are C₁-C₁₂alkyl, C₃-C₁₂alkoxyalkyl, C₄-C₁₆dialkylaminoalkyl or C₅-C₁₂cycloalkyl, or R₉ and R₁₀ together are C₃-C₉alkylene or C₃-C₉oxaalkylene or C₃-C₉azaalkylene, R₁₁ is C₁-C₁₈alkyl, C₂-C₁₈alkenyl or phenyl, R₁₂ is C₁-C₁₈alkyl, C₂-C₁₈alkenyl, phenyl, C₁-C₁₂alkoxy, phenoxy, C₁-C₁₂alkylamino or C₆-C₁₂arylamino or a group —R₂₄—COOH or —NH—R₁₇—NCO, R₁₃ is C₁-C₁₂alkyl, C₆-C₁₂aryl or C₇-C₁₄alkaryl, R₁₄ is C₁-C₁₂alkyl or phenyl, R₁₅ is C₂-C₁₀alkylene, C₄-C₅₀alkylene which is interrupted by one or more 0, phenylene or a group -phenylene-X-phenylene- in which X is —O—, —S—, —SO₂—, —CH₂— or —C(CH₃)₂—, R₁₆ is C₂-C₁₀alkylene, C₂-C₁₀oxaalkylene or C₂-C₁₀thiaalkylene, C₆-C₁₂arylene or C₂-C₆alkenylene, R₁₇ is C₂-C₁₀alkylene, phenylene, tolylene, diphenylenemethane or a group

R₁₈ is C₂-C₁₀alkylene or C₄-C₂₀alkylene which is interrupted by one or more O, R₁₉ is C₃-C₁₂alkanetriyl, R₂₀ is C₄-C₁₂alkanetetryl, R₂₃ is C₂-C₁₀alkylene, phenylene or a group

 wherein X is O, S, SO₂, CH₂ or C(CH₃)₂, and R₂₄ is C₂-C₁₄alkylene, vinylene or o-phenylene.
 2. An organic material according to claim 1, wherein the triazine compound (b) is a compound of the formula I in which n is 1 to 4, R₁ and R₂ independently of one another are H, OH or C₁-C₄alkyl, R₃ and R₄ independently of one another are H, OH, C₁-C₄alkyl, C₁-C₄alkoxy, halogen or a radical —OR₇, R₅ and R₆ independently of one another are H or C₁-C₄alkyl, R₇, if n is 1, is a) C₁-C₁₈alkyl which is substituted by one or more of the groups OH, C₁-C₁₈alkoxy, allyloxy, phenoxy, furyloxy,

 —COOR₈, —CON(R₉)(R₁₀) and/or by —OCOR₁₁, b) C₄-C₅₀alkyl which is interrupted by one or more O and can be substituted by OH or/and glycidyloxy, c) allyl, glycidyl or benzyl, d) cyclohexyl or hydroxycyclohexyl, and if n is 2, R₇ is C₄-C₁₂alkenylene, C₄-C₆alkenylene, xylylene, C₃-C₂₀alkylene which is interrupted by one or more O and/or substituted by OH, or R₇ is a group —CH₂CH(OH)CH₂O—R₁₅—OCH₂CH(OH)CH₂—, —CO—R₁₆—CO—, —CH₂—COO—R₁₈—OOC—CH₂— or

and if n is 3, R₇ is a group

and if n is 4, R₇ is a group

R₈ is C₁-C₁₂alkyl, C₃-C₁₈alkenyl, C₃-C₂₀alkyl which is interrupted by one or more O and/or substituted by OH or R₈ is C₁-C₄alkyl which is substituted by —P(O)(OR₁₄)₂, R₉ and R₁₀ are C₁-C₆alkyl or R₉ and R₁₀ together are pentamethylene or 3-oxapentamethylene, R₁₁ is C₁-C₁₂alkyl, C₂-C₅alkenyl or phenyl, R₁₄ is C₁-C₁₄alkyl, R₁₅ is C₂-C₈alkylene, C₄-C₅₀alkylene which is interrupted by one or more 0, or is a group

R₁₆ is C₂-C₈alkylene, C₂-C₆oxaalkylene or C₂-C₆thiaalkylene and R₁₈ is C₄-C₈alkylene or C₄-C₁₂alkylene which is interrupted by one or more O.
 3. An organic material according to claim 1, wherein the triazine compound (b) is a compound of the formula I in which n is 1, 2 or 4, R₁ and R₂ independently of one another are H or CH₃, R₃ and R₄ independently of one another are H, CH₃ or C₁, R₅ and R₆ are hydrogen, R₇, if n is 1, is a) C₁-C₁₄alkyl which is substituted by one or more of the groups OH, C₁-C₁₅alkoxy, allyloxy, phenoxy, furyloxy,

 —COOR₈, —CON(R₉)(R₁₀) and/or by —OCOR₁₁, b) C₆-C₄₅alkyl which is interrupted by one or more O and can be substituted by OH or/and glycidyloxy, c) glycidyl or d) hydroxycyclohexyl, and if n is 2, R₇ is C₆-C₁₂alkenylene, 2-butenylene-1,4, xylylene, C₃-C₂₀alkylene which is interrupted by one or more O or substituted by OH, or R₇ is a group —CH₂CH(OH)CH₂O—R₁₅—OCH₂CH(OH)CH₂—, —CO—R₁₆—CO—, —CH₂—COO—R₁₈—OOC—CH₂— or

and if n is 4, R₇ is

R₈ is C₄-C₁₀alkyl, oleyl, C₃-C₂₀alkyl which is interrupted by one or more O and/or substituted by OH, or R₈ is —CH₂P(O)(OR₁₄)₂, R₉ and R₁₀ are C₂-C₆alkyl R₁₁ is C₆-C₁₀alkyl, C₂-C₃alkenyl R₁₄ is C₁-C₁₄alkyl, R₁₅ is C₂-C₈alkylene, C₁₀-C₄₅alkylene which is interrupted by more than one 0, or is a group

R₁₆ is C₄-C₈alkylene and R₁₈ is C₄-C₈alkylene.
 4. An organic material according to claim 1, wherein the component (b) is a compound of the formula I in which n is 1 or 2 and, if n is 0.1, R₇ is a group —CH₂CH(OH)CH₂—OR₂, in which R₂₁ is C₁-C₁₈alkyl, allyl, phenyl, furyl, C₆-C₁₂alkanoyl or C₃-C₅alkenoyl and, if n is 2, R₇ is a group —CH₂CH(OH)CH₂O—R₁₅—OCH₂CH(OH)CH₂— in which R₁₅ is as defined in claim
 1. 5. An organic material according to claim 1, wherein the component (b) is a compound of the formula I in which R₁ and R₂ are hydrogen or methyl, R₃ and R are hydrogen, chlorine or methyl and R₅ and R₆ are hydrogen.
 6. An organic material according to claim 1, wherein the component (a) is a compound containing at least one group of the formula

in which R is hydrogen or methyl.
 7. An organic material according to claim 6, wherein R is hydrogen.
 8. An organic material according to claim 6, wherein the component (a) is one of the following compounds: Di-(2,2,6,6-tetramethylpiperidin-4-yl) succinate, Di-(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, Di-(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, Di-(1,2,2,6,6-pentamethylpiperidin-4-yl) butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)-malonate, Di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, Tetra-(2,2,6,6-tetramethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate, Tetra-(1,2,2,6,6-pentamethylpiperidin-4-yl) butane-1,2,3-,4-tetracarboxylate, N-(2,2,6,6-Tetramethylpiperidin-4-yl)-o-aminopropionic acid dodecyl ester, N-(1-Octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-N′-dodecyl-oxalamide N-(2,2,6,6-Tetramethylpiperidin-4-yl)-x-dodecylsuccinimide, 2,2,4,4-Tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane, 8-Acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetrarethylspiro[4.5]decane-2,4-dione, 20-(Dodecyloxycarbonylethyl)-2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro-[5.1.11.2]heneicosane, or a compound of the formulae


9. An organic material according to claim 1, which contains 0.01 to 5% by weight of the component (a) and 0.02 to 5% by weight of the component (b), relative to the material.
 10. An organic material according to claim 9, which contains 0.02 to 2% by weight of the component (a) and 0.05 to 3% by weight of the component (b).
 11. An organic material according to claim 1, wherein the material is an organic polymer.
 12. An organic polymer according to claim 11, which, in addition to the components (a) and (b) also contains further stabilizers, fillers, reinforcing agents, pigments, dyes, plasticizers, solvents, lubricants, flow-control agents, fluorescent brighteners, nucleating agents, antistatic agents or fire-retarding agents.
 13. An organic polymer according to claim 11, wherein the polymer is a coating binder.
 14. An organic material according to claim 1, wherein the material is a radiation-curable coating material.
 15. A radiation-curable coating material containing a hydroxyphenyltriazin of formula I as defined in claim 1 in the absence of a sterically hindered amine.
 16. A process for stabilizing organic material against damage caused by light, heat and oxygen by the addition of the components (a) and (b) as defined in claim
 1. 17. A compound of the formula Ia

in which n is 1 to 4, R₁ and R₂ independently of one another are H, OH, C₁-C₁₂alkyl, cyclohexyl or trifluoromethyl, R₃ and R₄ independently of one another are H, OH, C₁-C₁₂alkyl, cyclohexyl, C₁-C₁₈alkoxy or halogen and, in the event that n=1, can also be a radical —OR₇, R₅ and R₆ independently of one another are H, C₁-C₁₂alkyl or halogen, R₇, if n is 1, is a) C₁-C₁₂alkyl which is substituted by phenoxy (which is unsubstituted or substituted by C₁-C₁₈alkyl, C₁-C₁₈alkoxy or halogen) or by a group —COOR₈, —CONH₂, —CONHR₉, —CON(R₉)(R₁₀), —NH₂, NHR₉, —N(R₉)(R₁₀) or —O—CO—R₂₂, b) C₄-C₅₀alkyl which is interrupted by more than one O and can be substituted by OH or/and glycidyloxy, c) glycidyl or a group

d) cyclohexyl substituted by OH or —COR₁₁ e) a group —CH₂CH(OH)CH₂OR₂₁ f) a group —SO₂—R₁₃, g) a group —CO—R₁₂ and if n is 2, R₇ is a) C₂-C₁₂alkylene, b) C₄-C₁₂alkenylene, c) xylylene, d) C₃-C₂₀alkylene which is interrupted by one or more 0 and/or substituted by OH, e) a group —CH₂CH(OH)CH₂O—R₁₅—OCH₂CH(OH)CH₂—, —(CH₂)_(m)—COO—R₁₈—OOC—(CH₂)_(m)— (wherein m is 1-3) or

and if n is 3, R₇ is a group

 (wherein m is 1-3), and if n is 4, R₇ is a group

 (wherein m is 1-3), R₈ is C₃-C₂₀alkyl which is interrupted by one or more O, N or S and can be substituted by OH, or R₈ is C₁-C₄alkyl which is substituted by —P(O)(OR₁₄)₂, —N(R.)₁₀), or —OCOR₁₁ and/or OH, or R₈ is C₃-C₁₈alkenyl, glycidyl or C₇-C₁₁phenylalkyl, R₉ and R₁₀ independently are C₁-C₁₂alkyl, C₃-C₁₂alkoxyalkyl, C₄-C₁₆dialkylaminoalkyl or C₅-C₁₂cycloalkyl, or R₉ and R₁₀ together are C₃-C₉alkylene or C₃-C₉-oxaalkylene or C₃-C₉azaalkylene, R₁₁ is C₁-C₁₈alkyl, C₂-C₁₈alkenyl or phenyl, R₁₂ is a group —R₂₄—COOH or —NH—R₁₇—NCO, R₁₃ is C₁-C₁₂alkyl, C₆-C₁₂aryl or C₇-C₁₄alkaryl R₁₄ is C₁-C₁₂alkyl or phenyl R₁₅ is C₂-C₁₀alkylene, C₄-C₅₀alkylene which is interrupted by one or more 0, or R₁₅ is phenylene or a group -phenylene-X-phenylene in which X is —O—, —S—, —SO₂—, —CH₂— or —C(CH₃)₂— R₁₇ is C₂-C₁₀alkylene, phenylene, tolylene, diphenylenemethane or a group

R₁₈ is C₂-C₁₀alkylene or C₄-C₂₀alkylene which is interrupted by one or more O. R₁₉ is C₃-C₁₂alkanetriyl, R₂₀ is C₄-C₁₂alkanetetryl, R₂₁ is H, C₁-C₁₈alkyl, C₃-C₁₈alkenyl, phenyl, phenyl substituted by C₁-C₁₂alkyl, C₁-C₁₂alkoxy or halogen, or R₂₁ is C₂-C₁₉alkanoyl, benzoyl, C₃-C₁₈alkenoyl, furyl or a group

R₂₂ is C₂-C₅alkenyl, R₂₃ is C₂-C₁₀alkylene, phenylene or a group

 wherein X is O, S, SO₂, CH₂ or C(CH₃)₂, and R₂₄ is C₂-C₁₄alkylene, vinylene or o-phenylene.
 18. A compound of the formula Ia according to claim 17, in which n is 1 or 2, R₁ and R₂ independently of one another are H, OH, C₁-C₁₂alkyl or halogenomethyl, R₃ and R₄ independently of one another are H, OH, C₁-C₁₂alkyl, C₁-C₁₈alkoxy or halogen and, in the event that n=1, can also be a radical —OR₇, R₅ and R₆ independently of one another are H, C₁-C₁₂alkyl or halogen, R₇ is C₁-C₁₂alkyl which is substituted by phenoxy which is unsubstituted or substituted by C₁-C₁₈alkyl, C₁-C₁₈alkoxy or halogen, C₁-C₁₂alkyl which is substituted by —COOR₈, —CONH₂, —CONHR₉, —CON(R₉)(R₁₀), —NH₂, —NHR₉ or —N(R₉)(R₁₀), C₆-C₂₀alkyl which is interrupted by more than one O and is substituted by OH, glycidyl, cyclohexyl substituted by OH or —OCOR₁₁, a group —CH₂CH(OH)CH₂OR₁₉ or —SO₂R₁₃, if n is 1, and, if n is 2, is C₂-C₁₂alkylene, C₄-C₁₂alkenylene, xylylene, C₃-C₂₀alkylene which is interrupted by O and/or substituted by OH, or a group CH₂CH(OH)CH₂O—R₁₅—OCH₂CH(OH)CH₂— or —(CH₂)_(m)—COO—R₁₈—OOC—(CH₂)_(m)— in which m is 1-3, R₈ is C₃-C₂₀alkyl which is interrupted by O, N or S and/or substituted by OH, C₁-C₄alkyl which is substituted by —P(O)(OR₁₄)₂, —N(R₉)(R₁₀) or —OCOR₁₁ and/or —OH, C₃-C₁₈alkenyl, glycidyl or C₇-C₁₁phenylalkyl, R₉ and R₁₀ independently of one another are C₁-C₁₂alkyl, C₃-C₁₂alkoxyalkyl, C₄-C₁₆dialkylaminoalkyl or C₅-C₁₂cycloalkyl, or R₉ and R₁₀ together are C₃-C₉alkylene or C₃-C₉oxaalkylene or C₃-C₉azaalkylene, R₁₁ is C₁-C₁₈alkyl, C₂-C₁₆alkenyl or phenyl, R₁₃ is C₁-C₁₂alkyl, C₆-C₁₂aryl or C₇-C₁₄alkaryl, R₁₄ is C₁-C₁₂alkyl or phenyl, R₁₅ is C₂-C₁₀alkylene, phenylene or a group -phenylene-X-phenylene in which X is —O—, —S—, —SO₂—, —CH₂— or —C(CH₃)₂, R₁₈ is C₂-C₁₀alkylene or C₄-C₂₀alkylene which is interrupted by O, and R₁₉ is C₁-C₁₈alkyl, phenyl, phenyl which is substituted by C₁-C₁₂alkyl, C₁-C₁₂alkoxy or halogen, C₂-C₁₂alkanoyl, benzoyl or C₃-C₅alkenoyl.
 19. A compound according to claim 17 of the formula Ia in which n is 1 to 4, R₁ and R₂ independently of one another are H, OH or C₁-C₄alkyl, R₃ and R₄ independently of one another are H, OH, C₁-C₄alkyl, C₁-C₄alkoxy, halogen or a radical —OR₇, R₅ and R₆ independently of one another are H or C₁-C₄alkyl, R₇, if n is 1, is C₁-C₆alkyl which is substituted by —COOR₈, —COONHR₉, —CON(R₉)(R₁₀) or —OCOR₂₂, or R₇ is glycidyl, hydroxycyclohexyl or a group —CH₂CH(OH)CH₂OR₂₁, and if n is 2, R₇ is C₄-C₁₂alkylene, C₄-C₆alkenylene, xylylene, C₃-C₂₀alkylene which is interrupted by one or more O and/or substituted by OH, or R₇ is a group —CH₂CH(OH)CH₂O—R₁₅—OCH₂CH(OH)CH₂—, —CH₂—COO—R₁₈—OOCCH₂— or

and if n is 3, R₇ is a group

and if n is 4, R₇ is a group

R₈ is C₃-C₂₀alkyl which is interrupted by one or more O and can be substituted by OH or R₈ is C₁-C₄alkyl which is substituted by —P(O)(OR₁₄)₂ or R₈ is C₃-C₁₈alkenyl, R₉ and R₁₀ independently are C₁-C₈alkyl or cyclohexyl or R₉ and R₁₀ together are pentamethylene or 3-oxapentamethylene, R₁₄ is C₁-C₁₄alkyl, R₁₅ is C₂-C₈alkylene, C₄-C₅₀alkylene which is interrupted by one or more 0, or R₁₅ is a group -phenylene-X-phenylene- in which X is —O—, —CH₂— or —C(CH₃)₂—, R₁₈ is C₄-C₈alkylene or C₄-C₁₂alkylene which is interrupted by one or more 0, R₂₁ is H, C₄-C₁₈alkyl, allyl, phenyl, furyl, C₅-C₁₉alkanoyl or C₃-C₅alkenoyl and R₂₂ is C₂-C₅alkenyl.
 20. A compound according to claim 17 of the formula Ia in which n is 1 or 2, R₁ and R₂ independently of one another are H or CH₃, R₃ and R₄ independently of one another are H, CH₃ or C₁, R₅ and R₆ are hydrogen, R₇, if n is 1, is C₁-C₄alkyl which is substituted by —COOR₈, —CON(R₉)(R₁₀) or —O—COR₂₂, or R₇ is glycidyl, 2-hydroxycyclohexyl or a group —CH₂CH(OH)CH₂OR₂₁, and if n is 2, R₇ is C₆-C₁₂alkenylene, 2-butene-1,4-ylene, xylylene or C₃-C₂₀alkylene which is interrupted by one or more O and/or substituted by OH, or R₇ is a group —CH₂CH(OH)CH₂O—R₁₈—OCH₂CH(OH)CH₂—, —CH₂—COO—R₁₈—OOCCH₂— or

and if n is 4, R₇ is a group

R₈ is C₃-C₂₀alkyl which is interrupted by one or more O and can be substituted by OH or R₈ is —CH₂P(O)(OR₁₄)₂ or oleyl R₉ and R₁₀ are C₂-C₆alkyl R₁₅ is C₂-C₈alkylene, C₁₀-C₄₅alkylene which is interrupted by one or more 0 or is a group

R₁₈ is C₄-C₈alkylene, R₂₁ is H, C₄-C₁₅alkyl, allyl, phenyl, furyl, C₅-C₁₂alkanoyl or C₃-C₅alkenoyl and R₂₂ is C₂-C₃alkenyl.
 21. A compound according to claim 17 of the formula Ia in which n is
 2. 22. A process for stabilizing organic material, in particular organic polymers, against damage caused by light, heat and-oxygen, by the addition of an o-hydroxyphenyl triazine, which comprises adding at least one compound of the formula Ia according to claim
 15. 23. An organic material containing at least one compound of the formula Ia according to claim 17 as a stabilizer against damage caused by light, heat and oxygen.
 24. An organic polymer as a material according to claim
 23. 25. An organic material according to claim 23, containing 0.01 to 10% by weight of a compound of the formula Ia, relative to the material.
 26. A polycarbonate according to claim
 24. 27. An organic material according to claim 23 which is a radiation-curable coating material.
 28. The use of the compounds of claim 17 of the formula Ia as a stabilizer for organic materials, in particular for organic polymers.
 29. Use according to claim 28 as a stabilizer for polycarbonates.
 30. The use of the compounds of claim 17 of the formula Ia as stabilizer for radiation-curable coating material. 